Journal of Cleaner Production 223 (2019) 729e738

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Journal of Cleaner Production

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Economic and energetic assessment of different phosphorus recovery

options from aerobic sludge
Saba Daneshgar a, Armando Buttafava b, Arianna Callegari a, Andrea G. Capodaglio a, *
a
Department of Civil Engineering and Architecture, University of Pavia, 27100, Pavia, Italy
b
UNECO Srl, Academic Spinoff, 27100, Pavia, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Phosphorus removal from Wastewater Treatment Plant effluents is mandated by law under many cir-
Received 22 December 2018 cumstances, at the same time, the need for more efficient P recovery technologies in the form of valuable
Received in revised form reusable products is also increasing, with the aim of conciliating environmental quality as well as the
13 March 2019
element’s scarcity concerns. Several researchers have identified municipal wastewater as one of the most
Accepted 18 March 2019
Available online 18 March 2019
promising sources of phosphorus recovery, as other recovery pathways are often limited by leaks and
short-circuits in the P anthropic cycle. Presently, phosphorus is traditionally removed from wastewater
using chemical precipitation or biological methods, ending up in unusable products or excess sludge.
Keywords:
Phosphorus recovery
Chemical (nonmetallic) precipitation, under controlled condition, could constitute a sustainable
Calcium phosphate approach for achieving this goal, with the formation of struvite (magnesium ammonium phosphate
Struvite hexahydrate) or other calcium phosphate compounds, which have great potential of being used as fer-
Economic feasibility tilizers. In this study, experimental and pilot-test conditions for recovery of P-based fertilizers from
Energy issues aerobically treated sludge are analyzed, estimating at the same time the economic and energy conse-
Aerobic sludge quences of several process approaches on the treatment facility operation.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction is significantly growing as global population and individual food

Phosphorous (P) is an essential micronutrient in the global food
production chain, which excessive concentrations in wastewater
effluents, and subsequent accumulation in water bodies may lead
to eutrophication phenomena, threatening local water quality and
putting life of aquatic organisms in danger (Bendoricchio et al.,
1993; Capodaglio et al., 2003). P in varying concentrations can be
found in agricultural and municipal runoff, and in urban sewer
flows (Copetti et al., 2018; 2017; Capodaglio et al., 2016a), therefore
its removal from Wastewater Treatment Plant (WWTP) effluents is
nowadays mandated by law in specific circumstances, for which
adequate technologies (biological or chemical) are required: an
effluent TP of 2 mg/l is required by the EU Water Framework
Directive for plants of 10 000e100 000 p.e., and 1 mg/l for those
with >100 000 p.e. On the other hand, P is perhaps the most
essential element for agricultural production, the demand of which
* Corresponding author.
E-mail addresses: saba.daneshgar@unipv.it (S. Daneshgar), armando.buttafava@
unipv.it (A. Buttafava), arianna.callegari@unipv.it (A. Callegari), capo@unipv.it
(A.G. Capodaglio).
consumption increase. Unfortunately, P global reserves are limited,
and expected to be completely depleted in the not far distant
future, with estimates in the range of 100e300 years of residual
supply (Cordell et al., 2009; Mayer et al., 2016; Daneshgar et al.,
2018a).
The need for more efficient phosphorus recovery technologies
in the form of a valuable reusable product is increasing, with the
aim of conciliating environmental quality as well as scarcity con-
cerns. Several researchers have identified municipal wastewater as
one of the most promising sources of phosphorus recovery, as other
recovery pathways are often critically limited by leaks and short-
circuits within its anthropically modified cycle (Daneshgar et al.,
2018a). Therefore, in the framework of significant paradigmatic
changes in wastewater treatment (Capodaglio et al., 2016b;
Capodaglio, 2017), technologies have been studied and developed
recently, with the aim of substituting P removal (for purely water
quality protection issues) with P recovery (therefore including
water protection and resources and energy conservation objec-
tives) in municipal wastewater streams. Most initial studies were
aimed at obtaining a process compatible and readily applicable to
anaerobic digestion (AD) sludges (Battistoni et al., 2001; Yoshino

https://doi.org/10.1016/j.jclepro.2019.03.195
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
730 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
et al., 2003; Wu and Bishop, 2004; Britton et al., 2005; Iqbal et al.,
2008; Morse et al., 1998), as this is in fact the most used method for
sludge processing after wastewater treatment, today.
Presently, phosphorus is traditionally removed from wastewater
using chemical precipitation or biological phosphorous removal
(BPR) methods; mainly, however, it is usually removed in the form
of “undesirable” products, such as iron or aluminum phosphates,
that cannot be used as fertilizers, and need to be further processed
for disposal, or excess, high-P content biological sludge. Even
sludge produced from BPR treatment, despite typically receiving no
chemicals addition, is not always suitable for direct use as fertilizer
additive on agricultural land, under current European -and
national-legislations. Consequently, new technologies ought to be
developed, to recover phosphorus in form of a valuable product
that can be used somehow more directly and with greater benefit.
Chemical (nonmetallic) precipitation, under controlled condi-
tion, could be a sustainable approach for achieving this goal (Yang
et al., 2006; Daneshgar et al., 2019). While phosphorus removal
efficiency by precipitation is in general quite high, the heavy metal
content of the final product is an issue when using conventional
Iron (Fe) and Aluminum (Al) salts addition. On the other hand, the
alternative addition of Magnesium (Mg) and/or Calcium (Ca) in
stoichiometric ratios could lead to the formation of struvite (mag-
nesium ammonium phosphate hexahydrate) or other calcium
phosphate compounds, which have great potential of being used as
fertilizers (De-Bashan and De-Bashan, 2004; Le Corre et al., 2009;
Rahaman et al., 2014; Johnston and Richards, 2003).
Uncontrolled precipitation of these P-derived minerals in
WWTPs have been observed for many years and are considered an
operational problem when precipitation occurs uncontrolled in
pumps and pipes, forming rock-hard occlusions and damaging in-
stallations (Borgerding, 1972). However, when formed and precip-
itated under controlled conditions, these compounds can be
effectively recovered and utilized as fertilizers, due to their high
nutrient contents. Calcium phosphate compounds, due to their
lower solubility, are less favorable for fertilizer use compared to
pure struvite, which is a source of both phosphorus and nitrogen,
both very important for plants growth.
Some patented, commercially available technologies are nowa-
days available for this purpose, such as Ostara® (Ostara Nutrient
Recovery Technologies, Inc.) and Struvia™ (Veolia Water Technol-
ogies), both leading to struvite precipitation driven by stoichio-
metric Mg addition to raw wastewater and sludge dewatering
centrate, respectively. Although already applied in real scale, they
have some drawbacks that will be discussed in light of the analysis
of results achieved from this study.
In previous studies (Daneshgar et al., 2018b, c), extensive
experimental laboratory work was conducted on the possibility of
recovering P from aerobic sludge using alternatively struvite or
calcium phosphate (CAP) precipitation. The purpose of this paper is
to verify and pilot-test operating conditions in an actual plant that
could favor recovery of P-based fertilizers, verifying the outcome of
such operation and estimating at the same time the economic and
energy consequences of this process approach.
2. Theory and assumptions
Struvite precipitation is known to spontaneously happen in
alkaline environment (Parsons, 2001), with an overall reaction
influenced by many factors, among which pH, ionic molar ratios
and particularly the presence of Ca, as main influencing factor
(Pastor et al., 2008; Hao et al., 2008; Lee et al., 2013). Struvite is
basically formed by the reaction of Mg2þ, NHþ 3
4 , and PO4 with 6
molecules of water, however, among its various components,
HPO2
4 happens to be the most dominant form of phosphate in the
solution, due to its higher equilibrium constant in the reaction
þ
between PO3 2
4 and H (Doyle and Parsons, 2002). HPO4 may also
2þ
react with Ca , however, if present in sufficient amounts, forming
calcium phosphate. On the other hand, Ca2þ may also form calcium
carbonate, at high pH values. Therefore, the following expressions
represent the basic precipitation reactions occurring in such
systems:
Mg2þ þ NHþ 2
4 þ HPO4 þ 6H2 O4MgNH4 PO4 :6H2 O þ H
þ
(1)
þ
3Ca2þ þ 2HPO2
4 4Ca3 ðPO4 Þ2 þ 2H (2)
Ca2þ þ CO2
3 4CaCO3 (3)
Usually, struvite or calcium phosphate precipitation for phos-
phorus recovery is applied to anaerobic digestion sludges, where
the concentration of phosphorus is sufficiently high. However,
Angela et al. (2011) suggested the possibility of applying the pro-
cess to aerobic sludge for this purpose. In conventional biological
aerobic processes, sludge usually contains 2e3% phosphorus, not
high enough to achieve efficient phosphorus recovery by chemical
precipitation (Daneshgar et al., 2018a) Generally, in fact, it is sug-
gested that P concentration needs to be greater than 10 mg/l for
effective struvite precipitation (Desmidt et al., 2015). However,
during enhanced biological phosphorus removal (EBPR) processes,
initially observed over 50 years ago in South Africa by pioneer
wastewater researcher James Barnard, P release may take place in
an anaerobic stage preceding the aerobic tank of an activated
sludge process, followed then by “luxury P uptake” (i.e. uptake in
much greater than stoichiometric ratio) in the aerobic zone itself,
under appropriate conditions (Levin and Shapiro, 1965; Barnard,
1976). This sudden surge in cellular P concentration could consti-
tute an opportunity for implementing phosphorus recovery in
WWTPs without, or prior to, anaerobic sludge digestion. Therefore,
combination of an optimized and controlled EBPR system with
chemical precipitation of released excess P, could potentially lead to
efficient P recovery.
The study was carried out at a large municipal WWTP near the
city of Milan, Italy. The plant, serving the southern sector of the city,
with capacity of about 1.25 million P.E., and average flow rate of
over 430000 m3/d, consists of a biological treatment line with
denitrification/nitrification process followed by aerobic sludge
stabilization, and therefore lacks the typical anaerobic sludge
digestion phase. In this situation, therefore, the possibility of
implementing phosphorus recovery directly from aerobic sludge
could be a great asset. The facility currently produces approx.
50 000 tons of sludge annually, with as estimated P content of
about 1400 tons/year. Anaerobic conditions in the pre-
denitrification basins, as well as some observed P uptake in the
subsequent aerobic zone, caused by low organic loading conditions,
are naturally present at times. Thus, the plant has great potential for
inducing optimized and well-controlled EBPR conditions, and
consequently to represent a suitable environment for struvite/cal-
cium phosphate precipitation. Furthermore, during previous
experimental laboratory studies conducted on the same plant
(Daneshgar et al., 2018b), it was observed that the P concentration
in the mixed liquor from the oxidation tank could reach up to
37 mg/L after being subjected to 1e2 days of continuing anaerobic
conditions in a separate “side-stream” holding volume; this
seemed to be sufficiently high for attempting to implement a side-
stream phosphate precipitation process.
Chemical equilibrium modeling software was preliminary used
to model equilibrium conditions of the above reactions in a wide
range of operating conditions of the facility considered. The
 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738 731

software PHREEQC, designed to calculate ion speciation and satu-

ration index (an indicator used to investigate the possibility of a
solid phase precipitating in a given solution), values of possible
precipitation products in given process operating conditions, was
selected and applied (Parkhurst and Appelo, 2013). A detailed
description of the simulations conducted to identify optimal con-
ditions for P precipitation is contained in Daneshgar et al. (2018b).
The most significant parameter identified by those calculations,
the Saturation Index (SI), is basically defined as the ion activity
product of the constituent ions, over their equilibrium solubility
product. If the value is positive (SI > 0) the solution is supersatu-
rated, and precipitation occurs, if negative the solution is under-
saturated, and precipitation does not happen. SI ¼ 0 indicates a
system at chemical equilibrium.

3. Materials and methods

The extensive array of laboratory experiments previously con-

ducted to assess the impact of different reaction parameters on the
efficiency of P precipitation processes (Daneshgar et al., 2018c) was
used to empirically determine the domain, in terms of values of the
various parameters, of the tests herein described.
The initial Ca:P ratio of the aerobic sludge originating from the
plant investigated was around 2, which is considered quite high. At
this ratio, Ca can be considered a very competitive ion and may
significantly affect the efficiency of precipitation by promoting ACP
or calcite production (Hosni et al., 2008; Da Cruz et al., 2017). The
authors, therefore, planned and conducted several lab-scale ex-
periments at different Mg:NH4:P molar ratios, at different pH levels
between 8.5 and 9.5, in order to observe the effect of different re-
action parameters on the efficiency of precipitation. Solutions’ pH
was adjusted initially using a NaOH buffer, later a cheaper buffer
agent, a Ca(OH)2 solution. Final precipitates were analyzed using
Fourier Transform Infrared (FTIR) spectroscopy (Perkin Elmer 1600
series, Waltham, MA, USA), Thermal Gravimetric Analysis (TGA)
(Mettler Toledo TGA 1 STARe System, Columbus, OH, USA), Induc-
tively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES)
(Perkin Elmer Avio 500 ICP-OES, Waltham, OH, USA) and Elemental
Analysis (Perkin Elmer 2400 CHNS/O Series II, Waltham, OH, USA).
To practically investigate the possibility and feasibility of
recovering phosphate in the form of valuable and useful products at
large scale, a pilot reactor was built and tested, with a volume of Fig. 1. Pilot-scale side-stream precipitation reactor scheme.
200 L operated in sequencing batch mode (Fig. 1). The reactor was
operated as a side-stream process of the main liquid treatment line,
4. Results
fed with mixed liquor from the oxidation tank with pH controlled at
the desired level using an automated PID-time proportional control
In the first part of the precipitation study, the Mg:NH4:P molar
system at two stages, as indicated in Fig. 1: first, at the top of the
ratio of the solution was adjusted to 5:5:1, based on the previous
reactor, by locally mixing buffer solution with the incoming liquor,
lab-scale test results. This specific molar ratio was the only one
then, in the reaction zone within, adding it to the volume under
allowing, as verified theoretically and practically, some precipita-
processing, to avoid pH reduction due to ongoing acidification
tion of struvite. For pH adjustment, NaOH solution was used, setting
processes (Le Corre et al., 2005; Muhmood et al., 2018). The reaction
the pH during the tests at two values of 8.5 and 9.0. The buffering/
zone was kept well-mixed by low-level aeration with low-flow
balancing solution was fed to the side-stream reactor at different
diffusers, these, however, could be easily substituted by low-
flow rates in different tests. For each test, the mixed liquor was
energy mechanical mixers. The added solution was prepared
allowed to react for a period variable from 1 to 3 HRTs. Results
based on the characteristics of the aerobic liquor, in order to adjust
indicated that a 60 min’ HRT would be sufficient to complete the
it to the desired Mg:NH4:P ratios.
precipitation reaction (Fig. 2a). Obtained precipitates were the
In addition to the precipitation tests carried out at different
analyzed by FTIR spectroscopy and TGA to determine the nature of
Mg:NH4:P ratios, an additional variable was introduced by applying
the solid phases precipitated, consisting in a mix of mostly struvite
Ca(OH)2 for pH adjustment, as a cheaper pH adjustment buffer than
and ACP, with some impurities. Average P recovery from triplicate
NaOH. Also in this case, a series of precipitation tests at variable
analytical assays was determined as 61.2% and 90.4% at pH ¼ 8.5
cationic ratios was carried out and, interestingly, it was observed
and 9.0, respectively.
that an ACP-rich precipitate could also be obtained under these
In the second part of the study, the Mg:NH4:P ratio was kept
circumstances, by keeping pH between 8.5 and 9.0.
732 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
Fig. 2. Total precipitates obtained from pilot tests. a) experiments with Mg:NH4:P of 5:5:1 and NaOH, b) experiments without Mg,NH4 addition.
unaltered at the original influent level, and no chemicals were
added to the system to modify ions content, to verify the possibility
of obtaining ACP precipitate without chemicals addition. The re-
actor’s HRT was fixed at 60 min, based on previous tests. The
reactor content pH was adjusted first at pH ¼ 9.0 using NaOH buffer
solution, and then at pH ¼ 8.5 and 9.0 using a Ca(OH)2 solution,
based on previous lab-scale results, which showed potential of
obtaining noticeable ACP-rich precipitates as final products in these
conditions. Results showed that phosphorus was recovered from
the reactor at 82.65% using NaOH at pH ¼ 9.0, and by 75.29 and
87.24% when using Ca(OH)2 at pH ¼ 8.5 and 9.0, respectively
(Table 1). Based on FTIR results, the final precipitates showed
composition patterns very similar to the ACP-rich precipitates ob-
tained during previous lab-scale experiments. These tests could
therefore promote the idea of recovering phosphate through ACP
precipitation as an economic alternative to pure struvite precipi-
tation, difficult to achieve in normal conditions (Daneshgar et al.,
2018c) in the case of aerobic sludge.
5. Discussion
Based on operating and stoichiometric conditions of the labo-
ratory tests carried out with the aerobic sludge, it was observed
that struvite, amorphous calcium phosphate (ACP), Calcite (CaCO3)
and monetite (CaHPO4) were the only phases that could possibly
precipitate in the considered system, demonstrating positive SI
values, as determined with the chemical equilibrium model.
However, based on actual infrared spectra of the obtained pre-
cipitates, monetite was never observed in any of the experiments,
therefore, it could be expected that the bulk of final precipitates
would consist of only struvite, ACP, calcite or a mixture thereof,
depending on specific operating conditions of each test.
Furthermore, the results showed that to finally obtain signifi-
cant struvite precipitation, high amounts of Mg and NH4 would
Table 1
Summary of side-stream reactor precipitation studies.
Ionic molar ratio Mg:NH4:P Buffering agent pH
5:5:1 NaOH 8.5
9.0
as in incoming WW NaOH 9.0
Ca(OH)2 8.5
9.0
need to be added to the system (in order to achieve the prescribed
ratios Mg:NH4:P > 3:3:1). High N:P ratios do in fact naturally
improve struvite precipitation over calcium phosphate’s
(Capdeville et al., 2013), therefore the aerobic sludge concentration
of NH4, normally considerably lower than its anaerobic counterpart,
would need to be supplemented. Due to the presence of calcium in
high amounts, also strong Mg addition would be needed to over-
come the latter’s competitive effect favoring calcium phosphate
precipitation. Consequently, obtaining pure struvite product from
aerobic sludge, no matter how rich in P, might not be economically
feasible due to excessive chemicals addition (Mg, NH4) demands. In
practice, this also occurs in the application of the mentioned
Ostara® and Struvia™ processes, which effectiveness is under-
mined by the high costs of chemical addition and pH control.
It was furthermore observed that an ACP-rich precipitate could
however be obtained if the solutions’ pH was kept below 9. Above
this pH level, high calcite precipitation occurred and, this not being
a favorable product for fertilizer use, resulted in an undesirable
outcome. It was also observed, on the other hand, that even without
Mg and NH4 addition it was still possible to obtain ACP-rich pre-
cipitates, still favorable to fertilizer industry use, although not as
valuable as pure struvite (Johnston and Richards, 2003).
5.1. Economic and energy feasibility of phosphate recovery from
aerobic sludge
The main economic obstacle for phosphate recovery through
struvite or calcium phosphate precipitation processes is usually the
operating cost of the reaction (Egle et al., 2016), dependent mainly
on the quality and quantity of chemicals required to be added to the
system. Initial P concentration in the influent, and P recovery effi-
ciency of the system are also important (Crutchik and Garrido,
2011; Dockhorn, 2009): higher initial values of both parameters
mean higher precipitation, thus more final product available as
Buffering agent needed (g/m3 treated) P recovery Type of precipitate
90 90.4% Mixed (mostly ACP)
150 61.2% Mixed (mostly ACP)
93 82.6% ACP
71 75.3% ACP
125 87.2% ACP
 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
fertilizer.
In the case of aerobic sludge considered in this study, it was
observed that both Mg and NH4 needed to be added to the solution
in ratios higher than 3 times the initial P concentration in the liquor,
to achieve struvite precipitation. This, inevitably, makes the process
economically unfeasible. The current commercial prices of
MgCl2$6H2O (magnesium chloride hexahydrate) and NH4Cl
(ammonium chloride) normally used as sources of Mg and NH4, in
fact, are around 0.123 Euro/kg (Birnhack et al., 2015; Lahav et al.,
2013) and 0.221 Euro/kg (Vieira et al., 2010), respectively.
Considering a Mg:NH4:P ratio of 5:5:1 and the initial P con-
centration in the influent, the cost of Mg and NH4 addition to the
reactor would be around 0.12 and 0.05 Euro respectively for 1 m3 of
side stream liquor treated. In addition, the dosage of NaOH for pH
adjustment, estimated in the conditions of this study at 0.09 kg/m3
and 0.15 kg/m3 (to achieve pH ¼ 8.5 and 9.0, respectively), based on
current average cost of a NaOH solution (around 440 Euro/ton
(Birnhack et al., 2015; Lehmann et al., 2013), would add an extra
price tag of between 0.04 and 0.07 Euro/m3 of wastewater treated
at pH ¼ 8.5 and 9.0, respectively. Overall, this setup would bring
chemical addition costs anywhere between 69 and 79 thousand
Euro/day for a plant with characteristics similar to the one studied,
assuming to treat its entire flow (Table 2).
To evaluate if cost reduction was in fact possible, in the second
part of the study, the precipitation reaction was operated without
modification of the initial Mg:NH4:P ratio of the aerobic liquor,
therefore eliminating the need for Mg and NH4 addition, cutting a
significant amount of additives’ total costs. In this case, the addi-
tional cost of operation is represented just the pH adjustment re-
agent. Results showed that, to adjust pH at 9.0, 0.093 kg of NaOH
were needed per cubic meter of wastewater being treated, at a cost
of 0.041 Euro/m3 wastewater treated (about 13.5 thousand Euro/
day).
A further improvement of the overall process economics was
demonstrated possible by using Ca(OH)2 for pH adjustment
(instead of NaOH). Under these conditions, great potential for
achieving an economic phosphate recovery process were shown.
Between 0.071 kg/m3 and 0.125 kg/m3 of Ca(OH)2 were in fact
added to the sludge solution for pH adjustment. Ca(OH)2 is a much
less expensive reagent compared to NaOH, about 1/10th of the
former at around 45 Euro/ton (Woods et al., 1999), which means
that the cost of adding it to the process is around 0.003 euro and
0.006 euro per cubic meter of wastewater, to maintain pH ¼ 8.5 and
9.0, respectively. In this case, also, there is no need for Mg and NH4
addition, bringing down total chemical costs to between 1 and 2
thousand Euro/day. Therefore, this scenario could constitute an
even more sustainable, readily applicable solution. Table 2 sum-
marizes the list of chemical costs related to the tests conducted.
With the above indicated average daily inflow rate (430000 m3/
d), and average P influent concentration determined at 3.2 mg/L,
the daily P load to the plant is about 1400 kg/d, with a great
Table 2
Unit costs of chemical addition (V/m3 ww treated) for pilot study.
Additive With chemical addition to achieve
5:5:1 Mg:NH4:P ratio
pH ¼ 8.5 (NaOH) pH ¼ 9.0 (NaOH)
MgCl2$6H2O 0.12 0.12
NH4Cl 0.05 0.05
NaOH 0.04 0.07
Ca(OH)2 e e
Average P removal % 61.2 90.4
P-rich precipitate (g/m3 treated) 93.2 159.8
733
potential for recovery under all the various options tested. Based on
the results obtained in this study, a potential exists to obtain on
average 0.1 kg and 0.16 kg of P-rich precipitates (struvite) per cubic
meter of wastewater treated at pH ¼ 8.5 and 9.0, respectively, in
case of Mg and NH4 addition at 5:5:1 M ratio (Table 2 and Fig. 2a).
However, it was observed that using only NaOH or Ca(OH)2 as
pH buffers, without any addition of Mg and NH4 sources, similar or
even higher amount of precipitates could be obtained. NaOH at
pH ¼ 9.0 led to a P-rich precipitate weight of 0.176 kg/m3 treated,
while with Ca(OH)2 as buffering reagent, between 0.169 and
0.251 kg/m3 at pH ¼ 8.5 and 9.0, respectively, were obtained
(Fig. 2b). Considering the results of FTIR and TGA analyses, the
major fraction of this final precipitate was determined to be cal-
cium phosphate (Ca3(PO4)2), at about 75% with about 20.5% H2O,
and 3% possible carbonate components. Therefore, the potential of
phosphorus removal/recovery from side-stream processing under
these conditions is 0.03 kg P/m3 ww treated when using NaOH and
0.025e0.04 kg P/m3 when using Ca(OH)2.
The calculations reported above are based on the average
WWTP flow and current plant’s configuration. The results of this
study showed that an offline (side-stream) anoxic volume with 1e2
days HRT would be needed for effective P release from the oxida-
tion tank sludge, and a further 1-h HRT should be sufficient for the
completion of the crystallization reaction in a subsequent precipi-
tation process. Therefore, under these conditions, capital costs for
implementing phosphate recovery could be quite high for a facility
like the investigated WWTP, mainly due to the current lack of a
preliminary EBPR process, which would allow P to be released
anaerobically in the existing tanks in sufficient amounts. Under
current process conditions, in fact, an additional anaerobic stage of
about 0.8 Mm3 would be needed prior to the precipitation stage
(Amann et al., 2018), estimated based on observed tests and
assuming treatment of the entire incoming flow (Münch and Barr,
2001). A detailed study is being carried out concerning the possible
introduction of the EPBR process in the facility, which could take
advantage of converting some of the current excess nitrification/
denitrification volume (from preliminary estimations about 1/4th
of the existing one) to this purpose. Also, modification of P release
conditions by chemical or thermal treatment of a side-stream
current could improve process efficiency.
5.2. Additional considerations on the circular economy of obtained
products
It has been shown that most of the precipitate obtained under
considered experimental conditions is calcium phosphate
(Ca3(PO4)2), rather than struvite. Although the latter is the fertilizer
compound by excellence (considering also its N content), calcium
phosphate minerals have as well a significant fertilizer use poten-
tial, as they have low solubility and high P content (20% for single
superphosphate and 45% for triple superphosphate) (Vries et al.,
Without chemical addition (pH control only)
pH ¼ 9.0 (NaOH) pH ¼ 8.5 (Ca(OH)2) pH ¼ 9.0 (Ca(OH)2)
e e e
e e e
0.04 e e
e 0.003 0.006
82.6 75.3 87.2
176.5 168.7 251.4
734 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
2016). Struvite has undoubtedly some advantages over them, not
the least the fact that it contains both essential macronutrients for
plants, and has more consistent soil enhancing properties. Plant
availability of calcium phosphate products is in fact not consistent,
and depends on the technology and processes used to obtain it
(Egle et al., 2016). These products have generally poorer perfor-
mance in alkaline soils, and better in acidic soils (Egle et al., 2016;
Amann et al., 2018), however, plant P uptake from calcium phos-
phate fertilizers and struvite are both generally high (usually > 76%)
(Ro€ mer and Steingrobe, 2018).
Struvite recovered from WWTPs is not widely commercialized
at the moment, therefore, while it is difficult to obtain a precise
market value of struvite as a fertilizer product, sparse data are
nonetheless available. For instance, the price of struvite being
currently sold by Unitika Ltd (Japan), is around 220 V/ton as re-
ported by Münch and Barr (2001), who also report struvite prices at
300e500 AUS$/ton (191e318 V/ton) in Australia. Etter et al. (2011)
independently suggest a market value of 310 V/ton. Amorphous
calcium phosphate on the other hand, could be used to produce
triple superphosphate (TSP), currently sold at 498 V/ton (Desmidt
et al., 2015). This production process requires addition of phos-
phoric acid (H3PO4) to calcium phosphate, which of course adds
extra cost to fertilizer’s manufacturing, however, calcium phos-
phate could be also used as raw material for phosphate rock
replacement. The latter, depending on its extraction source, con-
tains between 27 and 36% P2O5 (Vries et al., 2016) and, according to
the World Bank (Desmidt et al., 2015; Woods et al., 1999) is being
sold at prices between 830 and 1120 V/ton P (224e400 V/ton).
Based on these considerations alone, it would seem that it might
still be more economically favorable for the fertilizer industry to
use phosphate rock as prime material since sludge-recovered P
could cost 2.2e8.8 V/kg P, depending on the implemented process
(Desmidt et al., 2015; Schaum, 2007; Roeleveld et al., 2004), while
average price of P-fertilizers for farmers is 1.9e3.3 V/kg P (Desmidt
et al., 2015). Precipitates, however, have the added advantage of
lacking cadmium contamination, which is an important emerging
issue with mineral phosphate rock that has not been widely
addressed so far (Terry, 2014; Sabiha-Javied et al., 2009; Kratz and
Schnug, 2016).
5.3. Sustainability and environmental benefits considerations
The main advantage in implementation of phosphate recovery
for WWTPs, however, is not from the value of the precipitated
product itself in the fertilizer market, since either of the possible
achievable ones (struvite and Calcium Phosphate) is still not
competitive with raw PR, at the moment. The real incentive would
instead consist in the savings that would be possible to achieve for a
WWTP using a controlled phosphate recovery process. Jeanmaire
and Evans (2001) reported that annual costs of removing unde-
sired struvite precipitates in pipes and machinery of unspecified
European WWTP facilities could sum up to 65000 Euro/year per
facility, which could be significantly reduced by applying a
controlled phosphate recovery process.
Also, comparing to conventional chemical P removal using
Ferric Chloride (FeCl3), the cost of chemical precipitation for re-
covery is considerably lower (Woods et al., 1999). Depending on
actual Ferric Chloride dosage (a Fe:P ratio > 1.5 would normally be
needed for effective P removal) the cost for conventional chemical
removal at 80% P removal efficiency, similar to the one observed in
this study, could range between 1.94 and 2.6 V kg1 Prem
(Thistleton et al., 2002; Paul et al., 2001) which is higher than the
one estimated in the present case-study, at 1.46 V kg1 Prem in case
of NaOH buffering and down to 0.12e0.14 V kg1 Prem in case of
Ca(OH)2 buffering, without Mg and NH4 addition.
In addition, implementing P recovery (rather than removal)
technologies could reduce sludge production by 2e8% (on dry
matter basis) according to Jeanmaire and Evans (2001), leading to
similarly proportional savings on sludge handling and disposal
costs (Li et al., 2019). Shu et al. (2006) suggested that total sludge
handling and disposal cost savings achievable by adopting similar
methods to those here exposed could be up to 11 AUS$/d (7.2 Euro/
d) and 623 AUS$/d (397 Euro/d) in WWTPs rated at 1000 m3/d and
55000 m3/d, respectively. Considering the high capacity of the
analyzed facility, this could roughly translate to 3119 Euro/d (about
1.14 million V/year) savings on sludge handling and disposal
(without considering the higher specific cost of sludge disposal in
Italy, compared to Australia). Woods et al. (1999), on the other
hand, suggested a possible sludge reduction of 11e16% for a plant
with BOD:P ratio of 40e60, and flow rate of 150000 m3/d, when
using side-stream P recovery combined with conventional biolog-
ical treatment. Considering the average BOD:P ratio of 48 observed
at this facility, and its average flow rate, the potential of reducing
sludge production by implementing a P recovery process is quite
high.
Another important aspect of P recovery from WWTPs is the
environmental benefit that it could bring by reducing the amounts
of P released to the environment that might cause eutrophication in
water bodies (Hernandez et al., 2010). Molinos-Senante et al. (2010)
calculated a “shadow price” (shadow pricing is commonly used to
refer to the assignment of a monetary value to an abstract com-
modity that is not ordinarily quantifiable as having a market price,
but needs to be assigned a valuation to conduct a cost-benefit
assessment) for P-precipitated products equal to 42.47 V/Kg P,
meaning that every Kg of phosphorus not released to the envi-
ronment, would be equivalent to a corresponding environmental
benefit of that amount.
Table (3) shows the potential costs and savings for a WWTP like
the one studied, potentially achievable by implementing of a P-
recovery process (without Mg and NH4 addition), excluding po-
tential profits from the sale of P-containing precipitates. Some of
these values were taken from literature and thus cannot be held
final in the specific situation, however, they might be suitable to
give an idea of the possible advantage of implementing a P recovery
technology based on a paradigm that strongly differs from current
practice. Two values are presented, one considering the “shadow
price” of removed P in the calculation, the other ignoring it. The
total environmental benefit of P recovery from wastewater is in fact
difficult to evaluate and is usually ignored in quantitative studies.
However, based on this estimate, on average 0.218 Euro/m3 of
wastewater treated could be benefited by the environment by
applying P recovery technologies (Hernandez et al., 2010). There-
fore, a potential environmental benefit of around 94000 V/d (about
34 Million V/year!) for a WWTP like the one herein considered
could be “gained” in case of implementing P recovery.
5.4. Energy considerations
Liquid-phase P recovery technologies reduce, in general, the
cumulative energy demand of WWTPs (Muhmood et al., 2018;
Woods et al., 1999), by reducing energy requirements for sludge
handling, and providing replacement of P-containing products that
generally outweigh the energy demand of P-recovery technology
(for example, the production of P-based fertilizer from phosphate
rock in fact requires at least 2.11 kWh/kg P) (Gellings and
Parmenter, 2004) and providing renewed resources: it was sug-
gested that, on average, P-recovery technologies could reduce cu-
mulative WWTP energy demand by 17.7% (Amann et al., 2018). The
average specific energy consumption of the analyzed facility is
estimated at around 0.266 kWh/m3 of wastewater treated at the
 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
Table 3
Potential cost () and savings (þ) for the considered WWTP by implementation of P-recovery process without chemical MG and NH4 addition, in V/d.
pH ¼ 9.0 (NaOH)
NaOH 17774
Ca(OH)2 e 1390
Saving on sludge handling and disposala þ3119
Potential savings as environmental benefitb þ94176
Savings on equipment cleaningc þ178
Savings on energy consumption þ3680
Balance þ83379
Balance excluding environmental benefit estimation 10797
a
based on pure proportionality with Shu et al. (2006) calculations.
b
based on “shadow prices” estimated by Molinos-Senante et al. (2010).
c
based on estimates by Jeanmaire and Evans (2001).
local energy cost of 0.178 V/kWh (0.67 Euro/m3) (Longo et al., 2016;
Mazzini et al., 2017), summing up to a total cost of around 20800
V/day for energy alone. P-recovery technology applied to such a
plant could therefore reduce energy costs by about 3680 V/day
(1.34 Million V/year) according to cited literature estimates. Levlin
and Hultman (2003) also suggested that there might be an up to
27% overall energy demand advantage between a P-recovering
biological plant, and a P-removing conventional WWTP with
chemical addition.
Table 4 shows a comparison between energy consumption of
WWTPs adopting different P removal/recovery technologies. These
values include electricity, energy for chemical addition, handling
and transportation of disposed sludge, and related fossil fuel re-
quirements. Implementing P recovery technologies in the form of
struvite or other fertilizer P-containing materials would potentially
have less energy requirements than conventional P removal treat-
ment using ferric chloride or ferric sulfate salts. Struvite production
would consume less energy than production of other P-containing
fertilizers such as triple superphosphate. Tests in this study show
great potential for reducing energy consumption in this or a similar
facility. In this case, costs were estimated solely based on electricity
and aeration/mixing requirement. Nevertheless, such a WWTP
would need an upgrade to EBPR treatment to optimize the condi-
tion for phosphate precipitation, and this may require noticeable
capital investment and energy balance recalculation.
As shown in this study, liquid-phase P-recovery technologies
achieving struvite or calcium phosphate precipitation could ideally
achieve 75e90% of phosphate recovery from a side-stream crys-
tallization reactor, however, despite the abovementioned advan-
tages in terms of energy and resources, available commercial
technologies generally attain less than 40% total P recovery
compared to the total influent phosphorus into the WWTP (Egle
et al., 2016; Amann et al., 2018; Levlin and Hultman, 2003), with
the rest of it ending up in the final sludge and/or WWTP effluent.
This is due to the fact that normally, only a small portion of the total
influent flow rate is, in practice, side-streamed to the crystallization
reactor, in order for the process to remain feasible in terms of
reactor volumes and capital costs. In addition, these technologies
Table 4
Unit energy consumption of P removal/recovery technologies (kWh/m3 ww treated) for the WWTP in the study (data based on Maurer et al., 2003; Siegrist, 1996; Henze et al.,
2002).
kg of P recovered/m3 Chemical removal by precipitation EBPR Struvite
ww treated with chlorides precipitation
Using NaOH
(0.03) 0.4083 0.2331 0.1749
Using Ca(OH)2
(0.025) 0.3402 0.1942 0.1457
(0.04) 0.5444 0.3108 0.2332
735
pH ¼ 8.5 (Ca(OH)2) pH ¼ 9.0 (Ca(OH)2)
e e
2438
þ3119 þ3119
þ94176 þ94176
þ178 þ178
þ3680 þ3680
þ99763 þ98715
þ5578 þ4539
could be efficiently applied only in WWTPs with implemented
enhanced biological phosphorus removal, with high P release in the
intermediate anaerobic stage of the process. Recovery rate thus
depends also on optimal anaerobic conditions of the implemented
EBPR process. The more P-release in the anaerobic zone, the more P
would be available for recovery. Fig. 3 shows the schemes of a plant
without EBPR process and the possible implementation scheme of a
P-recovery process in a WWTP with EBPR.
Table 4 shows a comparison summary between the current,
conventional chemical treatment using ferric chloride and the
methods applied in this study (including only chemical addition for
pH buffering, as addition of Mg and NH4 for struvite precipitation
appears to be economically unsustainable). It can be seen that the
proposed process has clear advantages over conventional precipi-
tation methods in terms of both chemical addition cost and energy
consumption, while achieving at the same time a very desirable
phosphorus removal efficiency. Furthermore, the final product of
this process has more immediate economic and agricultural values
compared to the sludge produced by conventional, metal salts
precipitation, which needs further processing and cannot be used
directly in agriculture because of its metal content.
Further studies are necessary to determine if the pre-
crystallization anaerobic volume could be reduced by enhancing
P release occurring within by thermal, chemical or other ancillary
methods, thus making the overall process more affordable and
easier to implement(See Table 5).
In view of the results achieved, side-stream precipitation of CAP
with the sole addition of Calcium Hydroxide as pH buffer seems to
be a better strategy for P recovery from aerobic sludges than pre-
cipitation of struvite, from the economic, energetic and sustain-
ability perspectives. Since P precipitation conditions are governed
by the same chemical equilibrium laws exploited in the earlier
mentioned commercial processes Ostara® and Struvia™, the
adoption of these technologies should be carefully evaluated
against possible alternatives herein illustrated.
Fertilizer production from ACP precipitate (w/ Precipitation of ACP w/o chemical
postprecip. processing) (Mg, NH4) addition
0.2415 0.1332
0.2012 0.1110
0.3220 0.1776
736 S. Daneshgar et al. / Journal of Cleaner Production 223 (2019) 729e738
Fig. 3. P-recovery process implemented A) on the side-stream of a WWTP without EBPR; b) the same process added to a WWTP with EBPR.
Table 5
Comparison summary of conventional chemical precipitation using ferric chloride and non-metal precipitation proposed in this study with pH-control only chemical addition.
Ferric Chloride precipitation
Fe:P > 1.5
P removal % 80
Chemical Addition (V/kg Premoved) 1.94e2.6
Energy Consumption (kWh/m3 treated) 0.34e0.54
6. Conclusions
Phosphorous recovery through precipitation of readily crop-
available P minerals from aerobically-treated sludge shows
considerable potential for both removing this non-renewable, finite
and irreplaceable element from effluents, reducing environmental
concerns for high phosphorus release in sensitive water bodies, and
recovering it, extending its future availability. With appropriate
process changes, they may eventually substitute current precipi-
tation removal processes based on metallic salts, when their ad-
vantages will be fully understood and validated by operators and
practitioners.
Application of technology capable of recovering P compounds
suitable for fertilizer production from aerobic sludge processing
facilities, however, are still not widely applied at full-scale due to
limitations linked mostly to the need of additional, large reactors if
EBPR is not already implemented in the process train. More
importantly, as shown in this study, operating costs of these pro-
cesses may be an issue, depending on the desired final products: in
fact, comparing struvite and calcium phosphate as the two most
common possible final products of such processes, calcium phos-
phate recovery implies considerably lower operating costs in the
face of ultimately similar specific P recovery potential.
This study showed great potential of recovering phosphorus
through chemical precipitation for the facility considered. The
overall degree of recovery depends on the flow through the side-
stream anaerobic tank and crystallization volume, which in turn
must be weighted under a cost-benefit minimization approach.
Further studies may identify additional methods to reduce the
necessary volumes by speeding up the P-release process. The
optimal final product that can be obtained from the studied process
is a calcium phosphate-rich precipitate, that could be used in the
fertilizer industry as a suitable substitute to mineral phosphate
rock. The operating costs of the process, in case of using Ca(OH)2 for
pH adjustment, are significantly lower than in case of struvite
production which needs both Mg and NH4 addition. In addition,
environmental and economic benefits (although some of contro-
versial financial estimation), reduction of cumulative energy
Precipitation with pH control only (without Mg, NH4 addition)
pH ¼ 9.0 (NaOH) pH ¼ 8.5 (Ca(OH)2) pH ¼ 9.0 (Ca(OH)2)
82.6 75.3 87.2
1.46 0.12 0.14
0.13 0.11 0.18
demand of facilities, reduction of sludge production and related
handling costs, savings on the O&M costs of equipment cleaning,
are all advantages of P-recovery process implementation to be
considered.
Funding
This study was supported by a research grant from the CARIPLO
Foundation (Milan, Italy) grant number 2014-0582 to the Univer-
sity of Pavia, Department of Civil Engineering & Architecture (P.I.
Prof. Andrea G. Capodaglio).
Acknowledgement
Mr. Daneshgar received full PhD scholarship support from the
abovementioned CARIPLO Foundation grant. The authors thank the
WWTP operator for access and for the possibility of conducting
extensive testing on the facility.
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