w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0

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On wet chemical phosphorus recovery from sewage sludge

ash by acidic or alkaline leaching and an optimized
combination of both

Sebastian Petzet a,*, Burkhard Peplinski b, Peter Cornel a

a
Institut IWAR, Technische Universität Darmstadt, Petersenstr. 13, 64287 Darmstadt, Hesse, Germany
b
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany

article info abstract

Article history: The advantages and drawbacks of existing wet chemical phosphorus (P) recovery tech-
Received 18 December 2011 nologies, their applicability to different types of sewage sludge ash (SSA) and the role of
Received in revised form the decay products of detergent zeolites as a source of reactive Al in SSA are analyzed.
28 March 2012 Since neither a purely acidic nor a purely alkaline treatment are able to provide satis-
Accepted 31 March 2012 factory technical solutions a wet chemical phosphorus (P) recovery process for sewage
Available online 12 April 2012 sludge ashes (SSAs) is investigated in detail that is based on a sequential treatment of SSA
with an acid and a base. As a result of an acidic pre-treatment, the P fraction of the raw
Keywords: SSA that was bound as e alkaline-insoluble e calcium phosphate (CaeP) is converted into
Phosphorus recovery aluminum phosphate (AleP). This newly formed AleP can be easily dissolved via alkaline
Sewage sludge ash treatment and then easily separated from the alkaline leachate via precipitation of CaeP.
Alkaline and acidic leaching The Al-component can be reused as precipitant for P-removal in waste water treatment
Calcium phosphate plants (WWTPs). The investigated process requires fewer chemicals than the direct acidic
Aluminum phosphate dissolution of all P-compounds contained in the SSA. This is due to the described rear-
Detergent zeolites rangement of the P component from CaeP to AleP. That such a rearrangement of P occurs
XRD analysis indeed was confirmed through a combination of XRD, ICP and XRF analyses together with
mass balance calculations. The present investigation proves that the process works for
very different types of SSAs: For Al-rich SSAs that come from WWTPs where Al-salt is
used for chemical P-removal the described sequential treatment process works best and
yields P-recovery rates as high as 70e77%. But even for SSAs from WWTPs where only
iron salt is used for chemical P-removal, a considerable amount of the reactive Al
necessary for the described P-rearrangement is supplied by decay products of detergent
zeolites, a hidden Al-source present in most SSAs produced in Europe.
ª 2012 Elsevier Ltd. All rights reserved.

* Corresponding author. Tel.: þ49 6151 164858; fax: þ49 6151 163758.
E-mail addresses: s.petzet@iwar-tu-darmstadt.de, sebastianpetzet@gmx.de (S. Petzet).
0043-1354/$ e see front matter ª 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2012.03.068
3770 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0
1. Introduction
1.1. On the economic and ecological impact of
phosphorus recycling
Phosphorus (P) is an essential plant nutrient that cannot be
substituted. A continuous input of P-fertilizers to soils is
required to sustain crop production for the growing world
population. Most P-fertilizers are gained from sedimentary
phosphate rock deposits that are a finite and non-
renewable resource. In this context, technologies are
developed that aim to recover P from different waste
streams. Sewage sludge and sewage sludge ashes (SSAs) are
significant sinks for P and the recovery of P from these
waste streams and its recycling could contribute to decel-
erating global P-flows.
1.2. Phosphorus in wastewater treatment
During wastewater treatment with chemical and/or enhanced
biological P-removal (EBPR) around 90% of the P-load in the
raw sewage (1.8 g P/(capita d)) is removed from the wastewater
and transferred into the sewage sludge. Around 40% of this P is
bound biologically (11% in the primary sludge and 30% as
physiological P in the biomass of the waste activated sludge).
Approximately 10% of the P leave the waste water treatment
plant (WWTP) with the effluent and the remaining 50% are
usually removed chemically (by adding Fe- or Al-salts), bio-
logically by EBPR or through a combination of both (Cornel,
2002).
1.3. Phosphorus recovery schemes
During SSA incineration, all inert material contained in the
sewage sludge is concentrated in the SSA and the waste
stream is reduced to w30 g/(capita d). Besides components
valuable for potential fertilizers such as P, Ca, Mg, and K SSAs
also contain undesired elements such as heavy metals, Al, and
Fe. The Al- and Fe-contents mainly depend on the P-removal
process applied in the WWTP, and one differentiates between
Al-rich and Fe-rich SSA (Schaum, 2007).
P-recovery processes generally aim (a) at separating heavy
metals from the valuable P and if possible (b) at converting P
either into a plant-available form for reuse as fertilizer or into
a raw material for the P-industry. There exist two categories
of P-recovery technologies: wet chemical approaches and
thermal approaches. Thermal approaches separate P and
heavy metals at temperatures of 1000e2000  C and transform
P into a plant-available form (Adam et al., 2009; Scheidig
et al., 2009) or into yellow phosphorus (Schipper et al.,
2001). Among wet chemical approaches, first of all, one
distinguishes between acid and alkaline dissolution
techniques.
In the case of acidic dissolution, P and some of the metals
are dissolved. Thus, after acidic leaching the dissolved P has to
be separated from the (heavy) metals in order to create a P-
recovery product with low heavy metal content. The separa-
tion of P and dissolved metal ions requires further energy or
chemical input.
2. Objectives of the present study
The four main objectives of this study are:
 To analyze the advantages and drawbacks of existing wet
chemical P-recovery approaches including their applica-
bility to different types of SSA.
 To examine the role of the decay products of detergent
zeolites as a source of reactive Al in SSA and to analyze
(adverse) consequences for the performance of known P-
recovery technologies as well as opportunities for new
approaches.
 To investigate in detail the new wet chemical P-recovery
process recently proposed by Petzet et al. (2011) and to
clarify its advantages and possible limitations in compar-
ison with other wet chemical P-recovery approaches.
 To further optimize this recently proposed P-recovery
process.
3. Advantages and drawbacks of existing
wet chemical phosphorus recovery approaches
The following section presents a survey of existing wet
chemical P-recovery approaches, focusing on estimates of
chemical demand, technical feasibility, and the assessment of
their applicability to different types of SSA that show large
differences in their chemical composition.
3.1. Phosphorus recovery technologies based on acidic
dissolution
The first step of all acidic wet chemical P-recovery technolo-
gies is an almost complete acidic dissolution of P at pH-values
<2. This process is unavoidably accompanied by a partial
dissolution of metals or their compounds. The amount of
dissolved metals depends on the composition of the raw SSA
(Fe- or Al-rich) as well as on the type and amount of the added
acid (HCl or H2SO4). Taking into account that in most SSAs the
P component is predominantly present in the form of calcium
phosphates (CaeP), aluminum phosphates (AleP), and iron
phosphates (FeeP), the chemical demand for such a ‘complete
acidic dissolution of P’ can be estimated as follows (Levlin and
Hultman, 2004):
Ca9 ðAlÞðPO4 Þ7 þ 21Hþ /9Ca2þ þ Al
3þ
þ 7H3 PO4 (1)
AlPO4 þ 3Hþ /Al
3þ
þ H3 PO4 (2)
Fe3 ðPO4 Þ2 þ 6Hþ /3Fe2þ þ 2H3 PO4 (3)
FePO4 þ 3Hþ /Fe3þ þ H3 PO4 (4)
Eqs. (1)e(4) show that the theoretical chemical demand for
a complete acidic dissolution of each of these P-compounds is
3 mol Hþ/mol P. However, in practice more acid is needed
since other acid-soluble components usually contained
in SSA, such as CaO, CaCO3, Ca(OH)2, MgO, Fe2O3, K2O, and
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0 3771

Al-compounds, are dissolved as well. Table 1 shows the Schaum (2007) reported a chemical demand of 600 g H2SO4/
amount of acid required for the dissolution of P from different kg SSA, i.e. 4.46 mol Hþ/mol P for the acidic dissolution and
SSAs according to the literature. However, an estimate of the 300 g NaOH/kg SSA, i.e. 3.04 mol OH/mol P(AleP) for the
chemical demand, the technical feasibility and applicability of alkaline precipitation, the latter being very close to the theo-
P-recovery technologies that are based on acidic dissolution of retical demand of 3 mol OH/mol P(AleP).
P has to take into account all following process steps. Thus, Since AleP cannot be directly reused as fertilizer, the
after acidic leaching the dissolved heavy metals have to be precipitated AleP may be dissolved by alkaline treatment
separated from the dissolved P in order to create a valuable followed by precipitation as CaeP (Takahashi et al., 2001a)
P-recovery product. Additionally, it is desirable to separate according to Eqs. (6)e(7).
especially Al and Fe as well, as these elements impair the  
quality of the recovery product. While Al is almost completely AlPO4 þ 4NaOH/4Naþ þ AlðOHÞ4 þPO3
4 (6)
released during acidic treatment, only a minor part of Fe
dissolves (Schaum, 2007). It is worth mentioning that the Al 4 /Ca3 ðPO4 Þ2
3Ca2þ þ 2PO3 (7)
content of SSA does not exclusively result from the addition of
Eq. (6) shows that for AleP dissolution another 4 mol OH/
Al-salts for chemical P-removal in certain WWTPs. On the
mol P are required. Altogether, this type of wet chemical P-
contrary, SSAs from countries where detergent phosphates
recovery process results in a total chemical demand of at least
have been replaced by zeolite A show a molar Al/P ratio of at
4.2 mol Hþ/mol P and 7 mol OH/mol P.
least 0.5/1 due to the presence of decay products of detergent
By liquideliquid extraction (PASCH-process (Pinnekamp
zeolites, a hidden Al-source in these SSAs.
et al., 2010)) and sulfidic precipitation (Franz, 2008), dis-
For the removal of cations from the acidic leachate different
solved heavy metals can be successfully removed from the
approaches are technically feasible, such as sequential
acidic leachate, however Al remains in solution. Conse-
precipitation (Takahashi et al., 2001b), liquideliquid extraction
quently, when the pH in the purified leachate is raised by
(PASCH-process (Pinnekamp et al., 2010)), sulfidic precipitation
adding CaO, at least 50% of the P do not precipitate as CaeP,
(Franz, 2008; Pinnekamp et al., 2010; Schaum, 2007), cationic
but as AleP e due to the Al supplied by the decay products of
ion exchange (Donatello et al., 2010; Franz, 2008), and nano-
detergent zeolites as mentioned above e and thus the value
filtration (Niewersch et al., 2009). Advantages and drawbacks of
of the recovery product is reduced. Alternatively, AleP may be
these five P-recovery processes are briefly discussed in the
separated by an additional sequential precipitation. For this,
following sections.
in a first step NaOH is added and AleP is precipitated and
In the case of sequential precipitation, in a first step H2SO4
separated. Then, the remaining P is precipitated as CaeP. The
is added, P and metals are dissolved (Ca precipitates as CaSO4),
separated AleP may be further converted to CaeP by adding
and the remaining solids are separated from the P-containing
NaOH and Ca2þ ions according to Eqs. (6)e(7) (Pinnekamp
acidic leachate. The separation of dissolved P from heavy
et al., 2010). As the NaOH demand for these reactions is
metals is achieved by raising the pH-value in the acidic
very high (Eqs. (5) and (6)), processes that do not remove Al
leachate to induce the precipitation of AleP while most heavy
from the acidic leachate before P is recovered by precipitation
metals remain in solution (Takahashi et al., 2001b). The heavy
are only suited for SSAs with low Al contents, i.e. for SSAs
metal content of the AleP product can be further decreased by
coming from WWTPs without Al-dosage for P-removal. And
precipitating heavy metals with sulfide (Schaum, 2007). Since
even in this case, around 50% of P will be recovered as low
the entire P has to be precipitated as AleP, this process can be
value AleP.
directly applied to Al-rich SSA coming from WWTPs that
The successful removal of all cations (including Al3þ) by
employ chemical P-removal by addition of Al-salts. The
a cationic ion exchanger was reported by Donatello et al.
amount of base needed for the sequential precipitation of P
(2010), though the authors provided no information on the
from the acidic leachate can be calculated as follows:
life time and regeneration of the columns, or how heavy
þ H3 PO4 þ 3OH /AlPO4 þ 3H2 O
3þ
Al (5) metals contained in the acidic back-wash water are dealt

Table 1 e Acid demand for the acidic dissolution of P from different SSAs; experimentally determined values; data from
Schaum (2007) are presented as mean values for the subgroups of 6 Ca-rich (line 1) and of 13 Ca-poor (line 4) SSAs.
No. Acid Number of Molar mol Hþ/mol P kg acid/ Dissolved P/ Author
investigated ratio P/Ca (mean value  esd) kg SSA total P [%]
SSA

1 HCl 5 0.25  0.07 14.1  4.3 0.68  0.19 95  3% Schaum (2007)

2 H2SO4 1 0.31 8.4 0.5 99.4% Franz (2008)
0.5
3 H2SO4 2 0.74 5.3 0.5 66.5% Franz (2008)
6.0 0.5 84.3%
4 HCl 10 0.92  0.16 4.5  1.1 0.45  0.11 91  6% Schaum (2007)
5 HCl 2 1.07 6.2 0.4 >95% Pinnekamp et al. (2010)
1.24 4.4 0.4
6 H2SO4 1 1.50 2.7 0.3 90% Takahashi et al. (2001a,b)
3772 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0
with. Donatello et al. (2010), Franz (2008) reported on the
removal of cations including Al3þ from the acidic solution,
however the regeneration of the columns was not considered
to be economically feasible. Investigations by Franz (2008),
Pinnekamp et al. (2010), Schaum (2007) concluded that ion
exchange is neither technical nor economically feasible.
Nanofiltration, i.e. the separation of P from multivalent
cations by membranes, works in principle, though results
reported so far are not satisfactory, since the membranes
retained too much P due to the high ionic strength of the acidic
leachate that was mainly caused by dissolved Al3þ (Niewersch
et al., 2009).
As a consequence, among all P-recovery technologies
based on acidic dissolution of P, today sufficient conclusive
data is only available for liquideliquid extraction, sulfidic
precipitation, and sequential precipitation. However, the first
two processes are limited to Fe-rich SSA and fail to remove Al
from the acidic leachate while sequential precipitation can
only be applied to Al-rich SSA and appears to consume
extensive amounts of NaOH, at least if CaeP is to be
produced.
3.2. Phosphorus recovery technologies based on direct
alkaline dissolution
An elegant and promising alternative to the acidic dissolution
of P followed by a separation of dissolved P from the dissolved
metals is a direct alkaline dissolution of P contained in the
SSA. In this case, only the amphoteric AleP compounds
dissolve (see Eq. (6)) while most (heavy) metals remain in the
SSA. In a following process step, the dissolved P can be
precipitated from the alkaline solution (pH > 13) as CaeP with
a very low impurity level, via the addition CaCl2 (see Eq. (7)).
It is worth mentioning that the amount of AleP directly
leachable via alkaline treatment depends on both the Al
content and the Ca content of the SSA (Schaum, 2007). In case
of SSA with very low Ca contents, a significant amount of P
can be dissolved by direct alkaline elution. An extraordinary
example for this is the WWTP of Gifu, Japan, that recovers 75%
of Ptotal in a full-scale wet chemical P-recovery plant by direct
alkaline elution from Ca-poor and Al-rich SSA (Nakagaw and
Gotou, 2010). The mean value of the P/Ca ratio calculated
from the composition of 6 Japanese SSAs published by
Ohbuchi et al. (2008) is 2.00 (0.23), a value significantly higher
than the average of 0.70 (0.35) calculated from the compo-
sition of 15 German SSAs published by Schaum (2007). To
illustrate the strong dependence of the percentage of alkaline-
soluble P on the Ca content, Fig. 1 depicts e among others e
data for 13 untreated raw SSAs representing a wide range of P/
Ca ratios.
In contrast to the situation in Japan, in Germany, the Ca
content of raw SSA is generally high due to the geological
conditions (hard drinking water). Consequently, merely
0e35% of the Ptotal can be recovered by direct alkaline elution,
even if Al has been added for chemical P-removal (Schaum,
2007). However, recently, for one German Al-rich SSA (Petzet
et al., 2011) showed that the amount of P that can be dis-
solved and recovered by alkaline leaching can be increased
from 25 to 67% by applying an acidic pre-treatment step that
above all removes Ca, i.e. without any dissolution of P. The
70%
alkaline leachable P / Ptotal
60%
50%
40%
30%
20%
10%
0%
0 1 2 3 4
P / Ca [mol/mol]
SSA-A1 pre-treated SSA-A2 pre-treated SSA-B pre-treated
SSA-C pre-treated 13 different raw SSA
Fig. 1 e Percentage of alkaline-leachable phosphorus to the
total phosphorus content versus the molar ratio of P/Ca for
four SSAs that underwent acidic pre-treatment of various
intensities for Ca-removal and for 13 raw SSAs measured
by Schaum (2007).
detailed analysis and further improvement of this new tech-
nology is the focus of the following sections.
4. Materials and methods
The four SSAs (A1, A2, B and C) investigated in the present
study were taken from four full-scale sewage sludge inciner-
ation plants in Germany. Their P content are between 7.9 and
10.9 wt% and represent a wide range of Al, Ca and Fe content,
see Table 2 and Fig. 2. Two of these four SSAs are Al-rich and
came from WWTPs that apply chemical P-removal with Al-
salts (A1, A2). SSA-A1 has the highest Al content of all four
SSAs and a relatively low Ca content, whereas SSA-A2 has
a somewhat lower Al but a very high Ca content (Fig. 2). SSA-B
and C come from WWTPs where only iron salts are used for
chemical P-removal (Fig. 2). The Al/P ratio (mol/mol) of SSA-B
and C is 0.65 and 0.58, respectively, which is close to the
theoretical minimum value of 0.5 mol/mol that can be calcu-
lated based on the daily detergent zeolite load (Smulders et al.,
2002) and the average P-load of 1.8 g/(capita d). Thus, it can be
concluded that the Al contained in these two SSA is almost
entirely derived from detergent zeolites. While SSA-B has
a very high Fe- but an average Ca content (like SSA-A1) SSA-C
has a somewhat lower Fe content but a very high Ca content,
see Table 2 and Fig. 2.
All SSA were used as received; in particular they were not
ground. All elution experiments were conducted with a solid
liquid ratio of 1:10 for 24 h in a shaker (Heidolph Promax 1020)
at room temperature. Eluates were separated by centrifuga-
tion at 40,695  g (centrifuge Sigma 3K30 Z3, rotor 12155; max.
20,000 rpm) and filtrated (0.45 mm, Schleicher and Schuell
ME25) before being analyzed with ICP-OES (Perkin Elmer,
Optima 3200DV) according to DIN EN ISO 11885 (1998). The
amount of leached elements was calculated from the amount
of recovered leachate and the concentration of the elements
determined with ICP-OES. In addition, aqua regia dissolution
(DIN EN 13346 (2000)) followed by ICP-OES measurements as
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0 3773

Table 2 e Chemical composition of the investigated SSAs determined via ICP-OES after aqua regia dissolution. See also
Fig. 2.
Sewage sludge ash P [g/kg] Ca [g/kg] Al [g/kg] Fe [g/kg] K [g/kg] Mg [g/kg]

A1 80 103 109 24 10 11
A2 110 149 77 15 13 17
B 79 98 45 130 12 12
C 83 158 42 95 9 14

Sewage sludge ash Cu [mg/kg] Zn [mg/kg] Pb [mg/kg] Ni [mg/kg] Cr [mg/kg] Cd [mg/kg]

A1 1050 1790 137 46 56 5

A2 907 2220 79 44 57 4
B 844 3810 239 95 254 5
C 1120 2290 309 74 97 4

well as XRF analyses were conducted for the raw SSA as well
as for SSA after various leaching steps. The pH in the leachates
was determined with a WTM pH 197-S and Mettler Toledo
InLab 1003 electrode.
X-ray fluorescence analyses (XRF) were carried out with
a MagiXPro instrument (Panalytical) equipped with a rhodium
sealed tube operated at 60 kV  60 mA and with crystal
monochromators. Before being analyzed by XRF, SSA powders
were compressed into the form of dense solid discs having
a diameter of 32 mm and a height of 4 mm.
In order to determine directly which crystalline
compounds were dissolved or newly formed, untreated and
treated SSA as well as the precipitated recovery product were
analyzed by X-ray powder diffraction (XRD). Samples
analyzed by XRD were gently pulverized and homogenized in
a mortar mill (Retsch) using an agate grinding set. XRD
measurements were performed on a Bruker-AXS D-5000
Theta-Theta-diffractometer in Bragg-Brentano geometry,
using a 1.0 mm aperture slit, a 0.1 mm receiving slit, a sample
spinner (0 or 15 rpm), copper Ka1,2 radiation with
40 kV  30 mA and a Si(Li) solid state detector. Specimens had
a diameter of 38 mm, a thickness of 1 mm, and were prepared
0 the added acid for each leaching step (see light gray circles and
SSA-A1 100
SSA-A2
SSA-B
20
SSA-C 80
A2
]
[%
by front-loading. Data were collected in the 2Q-range from 6
to at least 80 in steps of 0.02 using 10 s per step.
5. Results and discussion
SSA-A1, A2, B and C were eluted with HCl of different molar-
ities (solid-to-liquid ratio 1:10). After this pre-treatment the
acid was separated from the leached SSA by centrifugation
and the chemical composition of all acidic eluates analyzed by
ICP-OES. These results are given and discussed in Sections 5.1
and 5.2. The thus acidic pre-treated SSA then underwent an
alkaline treatment with 1 M NaOH (solid-to-liquid ratio 1:10) in
order to test if the amount of alkaline-leachable P has
increased after the acidic treatment as compared to a direct
alkaline leaching of the original SSA (see Tables 3 and 4).
These results are given and discussed in Section 5.3.
5.1. Acidic pre-treatment of sewage sludge ash
Figs. 3 and 4 (left) show for all four SSAs how the dissolution of
the elements P, Al, Fe and Ca (see vertical axis at the left)
advances as the pH decreases during the titration with HCl.
The same figures (left) also show the cumulative amount of
vertical axis at the right side from these data points). It can be
seen that in all four SSAs the dissolution of Ca occurs in the
entire pH range below pH ¼ 8. Above pH 3 the amount of
released Ca (and Mg, data for Mg not shown) is proportional to
the added amount of acid and the ratio lies between 2 and

40
O3

60 2.3 mol Hþ/mol (Ca þ Mg). This finding is in line with the
3
2O

[%

theoretical amount of acid which is required for the dissolu-

Fe

60 tion of different Ca and Mg compounds contained in the SSA

40 such as the CaeP compound of the whitlockite-type, CaO,
Ca(OH)2, (Ca, Mg)CO3 and MgO (see Eq.uation (1)).
80 In the case of SSA-A1 (Petzet et al., 2011) P, Al and Ca
20
simultaneously dissolve at pH-values <3. When the dissolu-
tion of P just starts, 90% of Catotal has already been dissolved.
100 The second Al-rich SSA-A2 which contains more Ca than SSA-
0
0 20 40 60 80 100 A1 starts to release P together with Al and Ca at a pH <3.4. At
this point 75% of Catotal have already been released. A simul-
CaO [%]
taneous release of P, Al and Ca can also be observed for the Fe-
Fig. 2 e Ternary plot of the four investigated SSAs. Circles rich SSA-B at a pH-value <3.2. However, in the case of SSA-B
symbolize Al-rich and triangles Al-poor SSAs. Black color 9.6% of the P dissolve before the simultaneous dissolution of
indicates higher Ca contents. See also Table 2. P, Al and Ca starts. Similar to SSA-B the Fe- and Ca-rich SSA-C
3774 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0
Table 3 e Comparison of the percentage of Ptotal [%] that can be dissolved either by a direct alkaline treatment or by an
alkaline treatment following an acidic pre-treatment. The molarities of the acidic pre-treatment are given in the right
column.
Sewage Directly
sludge ash alkaline-leachable P
A1 31%
A2 25%
B 29%
C 25%
releases some of the P at a higher pH-value (w4.6), without
a simultaneous release of Al. The simultaneous release of P, Al
and Ca starts at a pH value of <3.75 in almost the same
manner as in SSA-A1, A2 and B. At this point 23.6% of P is
already dissolved.
SSA-A1 releases 60 mmol/L Ca in the pH range of 3.0e2.2
where the dissolution of P occurs (see Fig. 3, left). If this
released Ca originated exclusively from a dissolution of CaeP
this would mean that e according to Eq. (1) e in this raw SSA
the dissolution of CaeP contributes 22% to the total amount of
dissolved P. Analogous calculations for SSA-A2, SSA-B and
SSA-C result in 22%, 33% and 62%, respectively. On the other
hand, if the released Al originated exclusively from dissolu-
tion of AleP this would mean that e according to Eq. (2) e the
dissolution of AleP contributes 72% (SSA-A2), 55% (SSA-B) and
47% (SSA-C) to the total amount of dissolved P. The sum of P
originating from dissolved CaeP and AleP is between 88 and
108% of Ptotal for SSA-A2, B and C and thus fits the stoichi-
ometry of a simultaneous dissolution of AleP and CaeP within
the uncertainty of measurement of z10%. At first glance this
semi-quantitative description of the simultaneous release of
P, Al and Ca suggests that in these four raw SSAs most of the P
is bound in the form of AleP and only a minor fraction as
CaeP. However this interpretation appears to be questionable
for the following three reasons:
 Although AleP are completely soluble in alkali, a direct alka-
line treatment of the four investigated SSAs dissolves no
more than 30% of their P content (Table 3).
 Generally, CaeP are soluble at pH <5 (Stumm et al., 1996).
However, a simultaneous release of Ca and P which would be
expected in the pH range of 5e4 is observed only for SSA-C,
while SSA-A1, A2 and B do not release Ca and P until a pH of
<3.4, <3.2 and 3.2, respectively (Figs. 3 and 4, left half).
 During wastewater treatment usually no more than 50% of
the removed P is precipitated with Al or Fe salts while the
rest is incorporated biologically (Cornel, 2002). SSA-B origins
from a WWTP that uses only Fe as precipitant and the only
possible source of Al in this SSA is zeolite A. Thus it appears
Table 4 e Chemical composition of the recovery product gained from SSA-A1 determined via ICP-OES after aqua regia
dissolution.
P [g/kg] K [g/kg] Mg [g/kg] Ca [g/kg]
152.9 0.08 0.20 297.5
Cd [mg/kg] Cr [mg/kg] Ni [mg/kg] Na [g/kg]
0.074 n.d. 0.203 35.6
Alkaline-leachable molHCl/kgSSA in acidic
P after acidic pre-treatment pre-treatment
60% 4
56% 6
44% 3
32% 5
implausible that as much as 55% of all P should be bound as
AleP after incineration at w850  C and a retention time of
just few seconds. Furthermore a formation of AleP during
anaerobic digestion as discussed by Jardin and Pöpel (1996)
provides also no explanation since none of the four inves-
tigated SSAs was anaerobically digested.
The apparent contradictions may be solved by an inter-
pretation recently proposed by Petzet et al. (2011): CaeP,
contained in the original SSA, in fact dissolves during the
acidic treatment as the pH decreases but the thus released P
is instantly precipitated by Al which is released during the
acidic titration as well. Such a rearrangement of P from CaeP
to AleP could well explain why no significant dissolution of P
is detected until at a pH of 3.0, i.e. until AleP starts to
dissolve.
5.2. XRD-analyses of untreated and acidic pre-treated
SSA
In order to test whether CaeP components indeed dissolve
during the acidic treatment before P is released into the acidic
eluate, XRD measurements were carried out on SSA-A1 and
A2 before and after these two SSAs underwent an acidic pre-
treatment with 4 and 6 molHCl/kgSSA, respectively. Previous
ICP measurements of the eluates had shown that at this acid
dosage, very little P is detected in the eluate (see Fig. 3, pH w 3),
while 62% (A1) and 72% (A2) of the initial Ca is leached from
the SSA. The XRD results show that e as expected e the
disordered AleP phase is not dissolved by this type of acidic
treatment (Fig. 5a and b). Furthermore, for SSA-A1 (see Fig. 5)
and A2 (not shown, but similar results) the results clearly
show that much of the crystalline CaeP (whitlockite) that can
be identified in the original SSA (Fig. 5a) is destroyed by acidic
leaching. However, remnants of whitlockite are still present
(Fig. 5b). Naturally, in the case of the dissolution of whitlock-
ite, a simultaneous release of Ca and P with a molar ratio P/Ca
w2/3 would be expected, which has not at all been observed
during this acidic treatment. These apparently contradictory
Fe [g/kg] Al [g/kg] Cu [mg/kg] Zn [mg/kg]
0.02 1.34 4.5 20.73
Mn [mg/kg] As [mg/kg] Pb [mg/kg] U [mg/kg]
1.26 27.93 3.374 2.043
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0 3775

500 10 250 10
Optimum pH for

alkaline soluble [mmol/L]

amount of HCl added in

pre-treatment [mol/kgSSA]
amount of HCl added in

pre-treatment [mol/kgSSA]
dissolution of
acid soluble [mmol/L] 400 8 200
Ca-P and
8
SSA-A1 formation of Al-P
300 6 150 6

200 4 100 4

100 2 50 2

0 0 0 0
1 2 3 4 5 6 7 8 1.5 2.5 3.5 4.5 5.5 6.5
pH of acidic pre-treatment pH of acidic pre-treatment
P - HCl Al - HCl Ca - HCl Fe - HCl amount of HCl P - HCl + NaOH Al - HCl + NaOH amount of HCl

500 10 250 10
Optimum pH for

alkaline soluble [mmol/L]

amount of HCl added in

amount of HCl added in

pre-treatment [mol/kgSSA]
pre-treatment [mol/kgSSA]
dissolution of
acid soluble [mmol/L]

400 8 200 8
Ca-P and
SSA-A2 formation of Al-P
300 6 150 6

200 4 100 4

100 2 50 2

0 0 0 0
1 2 3 4 5 6 7 8 1.5 2.5 3.5 4.5 5.5 6.5
pH of acidic pre-treatment pH of acidic pre-treatment
P - HCl Al - HCl Ca - HCl Fe - HCl amount of HCl P - HCl + NaOH Al - HCl + NaOH amount of HCl

Fig. 3 e Left side: Acidic leachability of P, Al, Ca, and Fe during acidic pre-treatment of the two Al-rich SSAs A1 and A2 at
different pH-values. Right side: Leachability of P and Al during subsequent alkaline leaching of the acidic pre-treated SSA.
The optimum pH for alkaline dissolution is indicated by a dotted circle. Results for SSA-A1 according to Petzet et al. (2011).

findings could be explained if assuming that the P that was be concluded that the newly formed AleP precipitate is X-ray
released by dissolving CaeP was instantly precipitated by Al. amorphous. Further XRD measurements showed that the
However, a new crystalline P-containing precipitate could not remaining whitlockite and the disordered AleP compounds
be identified in the XRD measurements. Consequently, it can are completely destroyed when treated at pH-values <3.

500 10 250 10
Optimum pH for
alkaline soluble [mmol/L]
amount of HCl added in
pre-treatment [mol/kgSSA]

amount of HCl added in

pre-treatment [mol/kgSSA]
dissolution of
acid soluble [mmol/L]

400 8 200 8
Ca-P and
SSA-B formation of Al-P
300 6 150 6

200 4 100 4

100 2 50 2

0 0 0 0
1 2 3 4 5 6 7 8 1.5 2.5 3.5 4.5 5.5 6.5
pH of acidic pre-treatment pH of acidic pre-treatment
P - HCl Al - HCl Ca - HCl Fe - HCl amount of HCl P - HCl + NaOH Al - HCl + NaOH amount of HCl
500 10 250 10
alkaline soluble [mmol/L]

pre-treatment [mol/kgSSA]
amount of HCl added in
amount of HCl added in
pre-treatment [mol/kgSSA]
acid soluble [mmol/L]

400 8 200 8
SSA-C
300 6 150 6

200 4 100 4

100 2 50 2

0 0 0 0
1 2 3 4 5 6 7 8 1.5 2.5 3.5 4.5 5.5 6.5
pH of acidic pre-treatment pH of acidic pre-treatment
P - HCl Al - HCl Ca - HCl Fe - HCl amount of HCl P - HCl + NaOH Al - HCl + NaOH amount of HCl

Fig. 4 e Left side: Acidic leachability of P, Al, Ca, and Fe during acidic pre-treatment of the two Fe-rich SSAs B and C at
different pH-values. Right side: Leachability of P and Al during subsequent alkaline leaching of the acidic pre-treated SSA.
The optimum pH for alkaline dissolution is indicated by a dotted circle.
3776 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0

a 5
Q
b5 Q
Q

intensity / a.u.
intensity / a.u.

Q
Q
Q
Q

0 0
10 20 30 40 10 20 30 40

diffraction angle / ° diffraction angle / °

c 5
Q d5 Q Q
intensity / a.u.

intensity / a.u.
Q

Q
Q Q
Q

0 0
10 20 30 40 10 20 30 40

diffraction angle / ° diffraction angle / °

Fig. 5 e Diffraction patterns of SSA-A1 after various treatments; a e ‘as received’; b e after direct acidic elution; c e after
direct alkaline elution; d e after acidic pre-treatment followed by alkaline elution; symbols: C e whitlockite; Q e quartz;
vertical arrows e crystallographically disordered aluminum phosphate.

5.3. Alkaline leaching of acidic pre-treated sewage
sludge ash
In order to directly test whether the P that must have been
released during the dissolution of CaeP and afterward refix-
ated as an XRD-amorphous precipitate, is in fact refixated in
the form of alkaline-soluble AleP, all acidic pre-treated SSAs
underwent subsequent alkaline treatment. For that purpose,
10 molNaOH/kgSSA was added to the SSA after each respective
acidic pre-treatment steps presented in the left half of Figs. 3
and 4.
For each of the four SSAs the results of this subsequent
alkaline treatment are depicted in the right half of Figs. 3 and 4
in such a way that they are shown directly to the right of the
results of the preceding acidic pre-treatment of the corre-
sponding SSA. It can be seen that considerably higher values
of the P release are achieved if the alkaline treatment is
combined with an acidic pre-treatment carried out at pH-
values between 5 and 3. This effect is observed for all four
SSAs, though to a different extent. After pre-treatment at pH-
values between 3 and 4 e as indicated by the dotted circle e
the amount of alkaline-leachable P reaches a maximum and
decreases again at lower pH-values in the acidic pre-
treatment. Table 3 compares for all four SSA the percentage
of alkaline dissolved P of Ptotal that can be realized by a direct
leaching to the maximum value that can be achieved by
a combination with an acidic pre-treatment under optimized
conditions. These results show that in the case of all four
investigated SSA the percentage of alkaline-leachable P is
significantly increased by acidic pre-treatment. However, this
beneficial effect is much more pronounced in the case of the
two SSAs originating from WWTPs that apply P-removal by
the addition of Al-salts (the alkaline P-removal increases from
31 to 60% (SSA-A1) and from 25 to 56% (SSA-A2)), while it is
less pronounced in the case of the two SSAs originating from
WWTPs that apply P-removal by the addition of Fe-salts (from
25 to 45% (SSA-B) and from 26 to 33% (SSA-C)). For this reason,
all further experiments for P-recovery that are described in
Section 5.4 were conducted just with the Al-rich SSAs, A1
and A2.
Figs. 3 and 4 (right) show that the amount of alkaline-
soluble AleP decreases again if the amount of HCl applied in
the acidic pre-treatment exceeds a critical value, 5 molHCl/
kgSSA in the case of SSA-A1 and SSA-C, 6 mol/kgSSA in the case
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0
of SSA-A2, and 3 molHCl/kgSSA in the case of SSA-B. This can be
explained by the fact that at higher HCl molarities an
increasing fraction of AleP is destroyed that consequently is
not available for subsequent alkaline dissolution. This inter-
pretation is supported by the increase of Al- and P-concen-
trations in the acidic leachate at higher HCl molarities (Figs. 3
and 4, left) and the fact that XRD measurements show the
disordered AleP compound to disappear after further acidic
treatment (results not shown). The XRD measurements also
show that the disordered AleP component disappears after
direct alkaline leaching (Fig. 5c) and after alkaline leaching
following an acidic pre-treatment (Fig. 5d).
Fig. 1 depicts a comprehensive compilation of experi-
mental data and clearly shows that the percentage of alkaline-
soluble P increases with an increasing P/Ca ratio in untreated
SSA. In this context it is worth recalling that ICP and XRF
measurements have shown that the acidic treatment of the
four SSAs investigated in this paper results in an increase of
the molar ratio P/Ca due to the dominant leaching of Ca.
Consequently, in Fig. 1 the symbols of the acid- leached SAAs
are shifted to the right with respect to the symbols of the
corresponding raw SSA.
5.4. Further optimization of the leaching procedure and
mass balances
The P-recovery rate for SSA-A1 and SSA-A2 can be further
increased by a second (acidic or neutral) leaching step that
washes out that fraction of the initial Ca content that had been
dissolved in the first acidic pre-treatment but remained trap-
ped in the pores of the dewatered SSA together with some
minor remnants of the acid used in the first acidic leaching e
even after centrifugation. Such an elimination of the dissolved
Ca prevents the formation of hydroxylapatite that would
otherwise form during the following alkaline leaching step
due to the reaction of the trapped Ca with the P released from
the alkaline dissolved AleP components. In the case of SSA-A1
and SSA-A2, a second leaching step with 0.01 molHCl/kgSSA and
H2O, respectively, increased the alkaline recovery rate from 54
to 67% (SSA-A1) and from 56 to 60% Ptotal (SSA-A2). Applying
higher molarities of HCl did not further increase the alkaline
P-recovery rate in the second leaching step (results not
shown). Likewise, after the removal of the alkaline leachate by
centrifugation some remnants of the alkaline leachate
together with a certain fraction of dissolved P remain in the
pores of the alkaline-leached SSA e which in turn can be
washed out by a second alkaline leaching step.
In order to set up a complete mass balance for SSA-A1 and
SSA-A2, these SSAs were treated with the optimal amount of
acid (4 molHCl/kgSSA for SSA-A1 and 6 molHCl/kgSSA for SSA-A2;
the values had been determined in previous experiments, see
Fig. 3, right). This acidic pre-treatment was followed by an
additional washing step with 0.01 mol/L HCl (SSA-A1) or H2O
(SSA-A2). Fig. 6a and b show that this washing step removes
a significant amount of Ca from the SSA. After this, the solid
residues of the SSA were treated twice with 1 mol/L NaOH.
Each of these leachates was recovered and analyzed with ICP-
OES. Additionally, aqua regia þ ICP-OES, XRF, and XRD-
analyses were conducted for the SSA after each leaching
step. Then, the analysis results of (a) the amount of elements
3777
that had been dissolved from the SSA, collected with the
leachate and determined by ICP-OES and (b) the amount of
elements that had remained in the SSA after the individual
leaching steps and were determined by aqua regia þ ICP-OES
and XRF analyses were compiled. Thereby, it was possible to
set up mass balances for SSA-A1 and SSA-A2. Data for SSA-A1
are depicted in Fig. 6 (data for SSA-A2 were similar and are
therefore not shown except in Fig. 6f). The amounts of
alkaline-recovered P after such a multi-step leaching proce-
dure are 74% (SSA-A1) and 77% (SSA-A2), while direct alkaline
leaching only allows recovery rates of 32% (SSA-A1) and 25%
(SSA-A2) (see Table 3). These data are semi-quantitative since
the sum of P released from SSA-A1 (22%) and A2 (22%) after the
optimal acidic pre-treatment e as determined in the first set of
experiments, see left half of Fig. 3 e and of the alkaline released
P is 96% (SSA-A1) and 106% (SSA-A2).
In case, H2SO4 e instead of HCl e was used for acidic pre-
treatment, the amount of Ca that was extracted from the
SSA and recovered with the acidic leachate was reduced to
only 4e8% of Catotal due to precipitating calcium sulfate
(hydrate). The alkaline P-solubility was reduced to zero, i.e.
a value much lower to what is achievable by direct alkaline
treatment with NaOH.
5.5. Phosphorus recovery from the leachate as calcium
phosphate and recycling of dissolved aluminum
Precipitation experiments for P-recovery from alkaline
leachate as presented by Petzet et al. (2011) showed that the
recovery product had very low heavy metal contents and
could directly be reused as a slow-releasing CaeP fertilizer or
raw product in the P-industry. Only arsenic (As) was found in
higher concentrations (28 mg/kg), though this is still below the
threshold of the German fertilizer act of 40 mg/kg. The CaeP
precipitated in this experiment was dried at 105  C. XRD-
analyses confirmed the formation of hydroxylapatite
Ca5(PO4)3OH with minor amounts of monohydrocalcite
CaCO3$H2O and sodium carbonate Na2CO3 (Fig. 7).
After the precipitation of CaeP, Al remains in solution and
could be recycled as precipitant in WWTPs. The results show
that the amount of recoverable Al is 1.35 molAl/kgSSA (SSA-A1)
and 1.60 molAl/kgSSA (SSA-A2) (see Fig. 6 and Table 2). With a P
content of 2.6 molP/kgSSA (SSA-A1) and 3.5 molP/kgSSA (SSA-
A2) and a beta-factor (molar ratio of added Al to chemically
removed P) of 1.5 for P-precipitation, the amount of dissolved
and recovered Al would be large enough to precipitate 35%
(SSA-A1) or 30% (SSA-A2) of the P-load of the WWTP from
where these SSAs originated. This amount could probably
cover most of the precipitant required for enhanced P-
removal.
5.6. Comparison with other wet chemical processes
The proposed new wet chemical P-recovery process was
named SESAL-Phos recovery process (sequential elution of
sewage sludge ash for aluminum and phosphorus recovery)
(Fig. 8). It is particularly suitable for SSA from WWTPs that use
Al as precipitant for chemical P-removal. All known recovery
processes that only remove heavy metals and Fe but not Al
from the acidic leachate (see Section 3.1) cannot be applied to
3778 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0

SSA-A1: 0.4 M HCl SSA-A1: 0.4 M HCl + 0.01 M HCl

Eluate ICP Eluate ICP
0,9
Aqua regia + ICP
a 0,9
Aqua regia + ICP
b

dissolved from SSA (sum)

dissolved from SSA (sum)

total content in raw SSA

total content in raw SSA
XRF XRF
0,7 0,7

0,5 0,5

0,3 0,3

0,1 0,1

-0,1 -0,1
Al Ca K Mg P Al Ca K Mg P

SSA-A1: 0.4 M HCl + 0.01 M HCl + 1 M NaOH SSA-A1: 0.4 M HCl + 0.01 M HCl + 2 * (1 M NaOH)
1,0 1,0
Eluate ICP Eluate ICP
Aqua regia + ICP
c Aqua regia + ICP
d

dissolved from SSA (sum)

dissolved from SSA (sum)

0,8 0,8
total content in raw SSA

total content in raw SSA

XRF XRF

0,6 0,6

0,4 0,4

0,2 0,2

0,0 0,0
Al Ca K Mg P Al Ca K Mg P
SSA-A1: 1 M NaOH SSA-A2: 1 M NaOH
1,0 1,0
Eluate ICP Eluate ICP
Aqua regia + ICP
e Aqua regia + ICP f
dissolved from SSA (sum)
dissolved from SSA (sum)

0,8 0,8
total content in raw SSA

total content in raw SSA

XRF XRF

0,6 0,6

0,4 0,4

0,2 0,2

0,0 0,0
Al Ca K Mg P Al Ca K Mg P

Fig. 6 e Mass balances for individual process steps and the entire optimized SESAL-Phos process for SSA-A1. Bars show the
fraction of the given element removed during the wet chemical treatment(s) indicated above each individual graphic.
f: values for the direct alkaline treatment of SSA-A2.

this type of SSA since the recovery product would contain

large amounts of AleP. This is exemplarily illustrated by the
5 results provided in the present paper for two SSA coming from
WWTPs that do not use Al as precipitant, i.e. for SSA-B and
4 SSA-C. Data on the left side of Fig. 4 show that as much as 55%
intensity / a.u.

(SSA-B) and 46% (SSA-C) of Ptotal would precipitate as AleP

3 from the acidic leachate after the pH value is increased
again e unless Al had been removed from the acidic leachate
before adding the alkaline.
2
In the following sections it is shown e theoretically and
experimentally e that the presented SESAL-Phos recovery
1 process requires less acid and less alkali than the SEPHOS
process (Schaum, 2007). Like the SESAL-Phos process, SEPHOS
0 is particularly suitable for Al-rich SSA, but includes a complete
10 20 30 40 50 acidic elution of SSA (i.e. complete dissolution of CaeP, AleP,
diffraction angle / ° and Al(OH)3) followed by a rise in the pH-value in order to
precipitate heavy-metal poor AleP that eventually is dissolved
Fig. 7 e Diffractogram of the precipitated CaeP. by alkaline treatment. The comparison of the experimentally
Vertical bar diagram [ hydroxylapatite Ca5(PO4)3OH; determined values for the chemical consumption of these two
black circles [ monohydrocalcite CaCO3$H2O; processes is straightforward as SSA-A1 was investigated by
vertical arrows [ sodium carbonate [ gamma-Na2CO3. Schaum (2007) as well as in the present paper.
 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0 3779

Sewage HCl NaOH CaCl2

sludge ash
pH ~ 3 pH ~ 13
Al-precipitant

2. 4. 6.

1. 3. 5.

acidic leached sewage Ca-P

leachate sludge ash

1. Acidic elution for Ca-P dissolution and simultaneous formation of Al-P

2. Separation of acidic leachate with dissolved Ca from heavy metals for neutralization and
reuse as process water
3. Addition of NaOH for dissolution of Al-P
4. Separation of the alkaline leachate from the rest ash
5. Precipitation of the recovery product and reuse of dissolved Al as precipitant for WWTPs
6. Separation of the Ca-P and reuse of the dissolved Al as precipitant

Fig. 8 e Simplified process scheme of the SESAL-Phos process.

The key reaction of the SESAL-Phos recovery process is the
rearrangement of P from CaeP to AleP, which proceeds in the
presence of a reactive Al-component, e.g. Al(OH)3. This reac-
tion can be illustrated by three individual reaction Eqs. (8)e(10)
or alternatively by the corresponding overall reaction Eq. (11):
3þ 
Ca9 ðAlÞðPO4 Þ7 þ 21HCl/9Ca2þ þ Al þ 7H3 PO4 þ 21Cl
6AlðOHÞ3 þ 18Hþ /6Al
3þ
þ 18H2 O
7Al
3þ
þ 7H3 PO4 /7AlPO4 þ 21Hþ
Ca9 ðAlÞðPO4 Þ7 þ 6AlðOHÞ3 þ 18Hþ /9Ca2þ þ 7AlPO4 þ 18H2 O
Thus, during the rearrangement of P from CaeP into AleP
acid is consumed only for the dissolution of CaeP (see Eq. (8)),
since the simultaneous formation of a new AleP component
releases enough Hþ (see Eq. (10)) to fully compensate the
amount of acid needed for the release of Al3þ (Eq. (9)). More-
over, the AleP component that from the very beginning has
been contained in the untreated raw SSA is not dissolved during
this type of acidic treatment, thereby contributing to acid
saving.
The P-rearrangement reactions (Eqs. (8)e(10) or alterna-
tively (11)) result in a theoretical acid demand of 2.6 mol Hþ/
mol Prearranged, while the experiments showed an acid demand
of 3.25 (SSA-A1) and 3.69 (SSA-A2) mol Hþ/mol Prearranged.
These somewhat higher values can be explained by the
presence of further components (e.g. CaCO3, CaO) in the SSA
that dissolve under the given conditions, as well. Related to
the total amount of recovered P, the experimentally deter-
mined acid demand of the SESAL-Phos process is e see Fig. 3 e
only 2.1 mol Hþ/mol Precovered (SSA-A1) and 2.2 mol Hþ/
mol Precovered (SSA-A2), an amount considerably less than the
acid demand of 6.5 (SSA-A1) and 4.4 (SSA-A2) Hþ/mol Pdissolved
needed for a complete dissolution of P for exactly these two
SSA according to Schaum (2007).
The experimentally determined NaOH demand of the
SESAL-Phos process is 4.46 (SSA-A1) and 4.10 mol OH/
mol Precovered (SSA-A2), an amount close to the theoretical
4.00 mol OH/mol Precovered, see Eq. (6). In case of the SEPHOS
process (Schaum, 2007), two figures have to be considered: If P
is recovered as AleP (which cannot be used as a fertilizer) the
(8) experimentally determined NaOH demand is 2.9 mol OH/
mol Precovered, whereas, if alternatively P is recovered as CaeP
an additional NaOH demand of 4.0 mol OH/mol Precovered is
(9)
required e see (Eq. (6)) e resulting in a total OH demand as
(10) high as 6.9 mol OH/mol Precovered.
Consequently, the SESAL-Phos process leads to a signifi-
cantly reduced specific chemical demand though the recovery
rate of 74e78% is lower than the recovery rate of 90% reported
(11)
for the SEPHOS process.
6. Conclusions
A detailed analysis of the advantages and drawbacks of
existing wet chemical P-recovery technologies, taking into
account their applicability to different types of sewage sludge
ash (SSA) shows that neither only an acidic nor only an
alkaline treatment are able to provide satisfactory technical
solutions. However, in the case of Al-rich SSA, a combination
of acidic and alkaline treatments proves to be superior to each
of the two individual approaches. An example for such a P-
recovery process that combines acidic and alkaline process
steps is the SESAL-Phos process. Its applicability to SSAs that
differ considerably in their chemical composition has been
demonstrated in the present investigation via numerous
experiments.
P-recovery rates as high as 78% can be achieved if this
process is applied to Al-rich SSA coming from WWTPs that
use Al for chemical P-removal. Thus, the process is especially
suitable for Al-rich SSA for which common wet chemical
recovery processes cannot be applied as they fail to remove Al
from the acidic leachate. The new process works equally well
3780 w a t e r r e s e a r c h 4 6 ( 2 0 1 2 ) 3 7 6 9 e3 7 8 0
for SSAs with low or high calcium contents. The process can
even be applied to SSA coming from WWTPs that employ
chemical P-removal by the addition of Fe. However, in this
case the recovery rate is limited to 50%.
It was shown that a large fraction of the P content of the
investigated four raw SSAs that was bound as calcium phos-
phate (CaeP) and therefore was alkaline-insoluble, is e as
a result of acidic pre-treatment e transferred into newly
formed aluminum phosphate (AleP). It was further shown
that this newly formed AleP component together with the
AleP that is already present in the untreated raw SSA can be
dissolved by alkaline treatment and finally recovered as CaeP,
with very low heavy metal contents. The Al-component
remains in solution and can be reused as precipitant in
WWTPs.
It was shown that such a rearrangement of P from CaeP to
AleP requires less acid than a complete dissolution of P by the
addition of acid followed by precipitation of the dissolved P
and Al as AleP. Thus, the SESAL-Phos process consumes even
fewer chemicals than the SEPHOS process which is also
especially suitable for Al-rich SSA.
The role of the decay products of detergent zeolites,
a sometimes ignored component in communal SSA, was
elucidated and mass balance calculations proved that they
may serve as an essential source of reactive Al.
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