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marie-line Daumer
National Research Institute of Science and Tec
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Environmental Technology
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ABSTRACT
ARTICLE HISTORY
A sustainable way to recover phosphorus (P) in swine wastewater involves a preliminary step of P
dissolution followed by the separation of particulate organic matter (OM). The next two steps are
rstly the precipitation of struvite crystals done by adding a crystallization reagent (magnesia)
and secondly the ltration of the crystals. To develop the process successfully at an industrial
scale, the control of the mechanisms of precipitation is the key point in order to obtain high
value-added products, that is, big struvite crystals easy to harvest and handle. Experiments with
process parameters optimized previously in a synthetic swine wastewater were performed on
real swine wastewater to assess the role of the OM on struvite crystallization. After 24 h, with a
pH increase to 6.8 only, 90% of the initial P was precipitated and 60% was precipitated as
struvite. 80% of the solid recovered was in the fraction > 100 m. The other forms recovered
were brushite, amorphous calcium phosphate, NaCl, KCl and OM. The inuence of OM on
struvite precipitation in acidied swine wastewater was negative on the reaction kinetics but
positive on the size of the struvite crystals. The presence of colloidal particles increased the size
of the struvite crystals but slowed down the kinetics due to the viscosity induced by the
repulsive force of the colloids. The maximum size of single struvite crystals (200 m) was
observed with the presence of particulate OM.
Introduction
The issues in the recycling of phosphorus (P) are double:
(i) the protection of a limited resource and (ii) the ght
against eutrophication by adapting the application of P
to the crop requirements which would minimize the
leaks to the aquatic environment. The main sources for
P recycling are animal wastes and wastewater sludge.
Struvite (MgNH4PO46H2O), a crystalline form obtained
from dissolved P of liquid efuents, is marketed as a fertilizer in Japan or in Canada. It is usually obtained from
the liquid phase of dewatering anaerobic digested
wastewater sludge by crystallization but it can be
obtained from livestock waste.[1] However, most of the
systems developed at an industrial scale recycle only
the dissolved P from urban or agro-industrial efuents
and are seldom applied to concentrated efuents such
as swine wastewaters. One of the main limitations for
the development of such a process to recycle P from
swine wastewater is that P is mainly in particulate form
(80%) in the wastewater and mixed with a high level of
biodegradable organic matter (OM).[2]
So, as described by Daumer et al.,[3] a sustainable way
to recover P from swine wastewaters involves a
CONTACT Marie-Line Daumer
marie-line.daumer@irstea.fr
KEYWORDS
Struvite; phosphorus
recovery; pig manure; swine
wastewater; organic matter
A. CAPDEVIELLE ET AL.
Figure 1. OM fractionation.
Magnesia addition
The MgO suspension was prepared 1 h before the beginning of the run by mixing 10 g of MgO powder (97%,
VWR Prolabo) in 100 mL of distilled water. Magnesia
was kept in suspension under continuous stirring and
ENVIRONMENTAL TECHNOLOGY
Precipitation
Precipitation runs were performed in an FC6s occulator
from Velp Scientica. Each beaker was lled with 800 mL
of efuent. The addition of MgO was carried out under
continuous stirring at 90 rpm for 30 s. Then, the stirring
rate was maintained at 60 rpm for 24 h. Previous works
have shown that the optimal temperature for struvite
crystal growth was 5C.[4] However a low temperature
is difcult to apply in an on-farm processing plant. Therefore, reactions were carried out in beakers thermostated
at 15C, which is the annual average temperature in Brittany, by water circulating through a constant temperature bath. pH and temperature were recorded by an 8channel data logger pH/mV/Ion/O2 from Fisher Scientic.
The experiments were performed in duplicate
Sampling
Samples (4 ml) were collected from beakers at 15, 30, 45
min then at 1, 2, 3, 4, 6, 8, 22, and 24 h for dissolved com2+
2+
+
+
+
pound analysis (PO3
4 , NH4 , Ca , Mg , K , Cl Na ).
After 24 h, samples were sieved on 25 and 100 m
lters. The three solid fractions ( < 25 m, 25100 m,
and > 100 m) were dried at room temperature. Each
fraction was then weighed and analysed as described
below.
Analysis
Organic charge
The total chemical oxygen demand (TCOD) was analysed
using the French standard NFT 90-101. TCOD analyses
were conducted on the ASW (total, centrifuged and ltered) before and after the precipitation step. The total
solids (TSs), the total suspended solids (TSSs) and the
volatile suspended solids (VSSs) were measured using
the american standard methods.[14]
Solid and liquid characterization
The compositions of the collected solid fractions were
analysed by ionic chromatography after dissolution by
formic acid and the structure by X-ray powder diffraction
(XRD). The rates of the precipitation/dissolution of the
NH3 volatilization
Two beakers were reserved for the analysis of the NH3
volatilization in each experiment: one for the SSW and
one for the ASW. The volatilization of ammonia was evaluated from the difference between the concentration of
ammonium at 0 h and its concentration at 24 h after dissolution of the solid fractions with formic acid (80%) until
pH reached 4.5. The NH+4 /NH3 content was analysed by
distillation (method modied from NFT 90-015-1, Bchi
distillation unit B-324).
Particle analysis
The particle analysis was carried out with a morphogranulometer (Occhio, Flowcell FC200M) using an 800 m
thick measuring cell. The liquid is circulated continuously
in the measuring glass cell. For each measurement, 20
pictures were taken through the glass cell and analysed
in order to identify the number and the morphometric
criteria of each particle. The equivalent volume of each
picture is 4.04 L.
When the samples were clear enough, the particle
analysis was carried out directly in the beaker. This
method is called direct.
If the samples were heavily loaded with small particles, the method dilution was applied. The samples
were diluted using the liquid phase from centrifuged
samples (47,900 G, 20 min at the same temperature of
runs). The solid/liquid equilibrium was then maintained
avoiding the solid dissolution or crystallization due to
dilution.
For the morphometric analysis, Callisto 5.38 software
from Occhio was used. The struvite crystals were isolated
A. CAPDEVIELLE ET AL.
by applying a lter based on three shape factors: luminance, ISO circularity and ISO bre thickness. The luminance was in the range [00.45], the circularity in the
range [00.91] and the ISO bre thickness in the range
[1010,000].
Results
Initial conditions
The aim of the rst acidication/separation step was to
separate the P and the OM by dissolving mineral P
which is the main form in swine wastewater. In this
trial, dissolved P was increased from 312 to 928 mgP
L1. Ammonia was increased from 0 to 1233 mg L1. A
part of ammonia can be adsorbed on the biomass or precipitated as struvite.[16] Dissolution or desorption by the
acidication was responsible for this increase. About 85%
of the VS were removed and the VS/TS ratio in TASW was
reduced to 23% compared to 58% in treated slurry. The
sum of the ionic concentrations measured in this study
explained more than 85% of the dissolved mineral
matter composition (Table 1). At the end of the step,
OM estimated from chemical oxygen demand (COD)
was mainly dissolved (76%) and in particles (20%). Only
4% of the OM was in the colloid form as dened in this
paper. The COD due to formic acid addition was estimated by the concentration measured in synthetic efuent. However, a part of this oxidizing potential could
have been consumed by OM oxidation during acidication of the real efuent.
dt
Precipitation
Evolution of pH
In all the efuents, the pH increased from 4.5 to 6.1 in less
than 5 min. Then, the increase slowed down abruptly for
45 min only and speeded up again in SSW when it was
slowing down more progressively in all the ASW. After
(2)
(3)
1
NO
2 -N (mg L )
1
NO
3 -N (mg L )
1
-P
(mg
L
)
PO3
4
1
2
SO4 -S (mg L )
Na+(mg L1)
NH+4 -N(mg L1)
K+(mg L1)
Mg2+(mg L1)
Ca2+(mg L1)
pH
BTSW
TASW
CASW
FASW
SSW
40 3
23 2
27 3
2297 29
1.6 0.6
23.7 0.3
312 6
81 5
1112 18
00
1899 26
161 12
80 20
7.79
15 2
3.5 0.5
5.0 0.5
2108 28
14.1 0.5
0.9 0.8
928 19
69 1
1200 100
1233 20
2200 100
705 4
1289 25
4.35
4.0 0.3
5300 200
11.0 0.1
3.0 0.1
907 18
68 1
1100 100
1360 36
2100 100
718 10
1318 5
4.36
3.8 0.1
5700 100
12.0 0.1
4.0 0.1
1032 16
70 1
1300 200
1365 28
2200 100
726 5
1377 3
4.85
2.42 0.1
3864 59
26.8 4.2
6.7 0.8
1155 15
72 3
2301 26
1368 41
1764 27
563 7
1176 47
4.37
ENVIRONMENTAL TECHNOLOGY
Figure 2. pH variation during the entire test with a focus on the rst hours.
The concentration of phosphates precipitated as struvite during the reaction (PO4-PStruvite mmol L1) was calculated according to Equation (4). The ammonia
volatilization was below the quantication limits of the
methods ( < 5% of the NH4-N measured by distiller
Bchi). In those experiments struvite precipitation followed a rst-order kinetics after the latency phase
where [NH4-N] did not vary signicantly.
[PO4-P]t, [NH4-N]t, [Ca]t and [Mg]t are the concentrations of the removed phosphates, ammonium,
calcium and magnesium during the reaction (mmol
L1). [PO4-P]0/[NH4-N]0/[Ca]0 and [PO4-P]e/[NH4-N]e/[Ca]e
are the removed concentrations at the beginning of
the reaction and at equilibrium, respectively, (mmol
L1). [Ca]m and [Mg]m (mmol L1) are the maximum concentration of calcium removed and magnesium dissolved, respectively, reached during the run. KP, KN, KCa
and KMg (h1) are the kinetic constant of precipitation;
1/K is the time when the rst reaction is slowing down.
The precipitation rates of phosphates (yPO4 P mmol
L1 h1, (3)) of struvite (yPO4 PStruvite mmol L1 h1, (6)), of
calcium (yCa mmol L1 h1, (8)) and of magnesium (yMg
mmol L1 h1, (12)) are the asymptotes of the curves at
the beginning of the precipitations.
For all the regressions, the r was 0.99. Table 2 shows
the coefcient calculated by regression of the different
steps of the reaction.
The rst step was the precipitation of calcium phosphate and, in a less part, of struvite. For SSW and
FASW, the PO4-P precipitation rate in the rst minutes
was the sum of the calcium and struvite precipitation
rate. For TASW and CASW, the PO4-P precipitation rate
was higher than this sum. Phosphate might have precipitated with magnesium.
The second step was mainly due to the precipitation
of ammonium (or struvite) which started less than 5
min after the MgO was added for SSW and 1550 min
after the addition of MgO for the ASW. The precipitation
rate of struvite was low in TASW compared to in the
other efuents. We have previously observed that a
[NH3 N]volatilized ,
[NH4 N]t =([NH4 N]e [NH4 N]0 )
(1 eKN t ) + [NH4 N]0 ,
yPO4 PStruvite = ([NH4 N]0 [NH4 N]e ) KN .
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
A. CAPDEVIELLE ET AL.
Figure 3. Evolution of the ionic concentration during the entire test on the left with a focus on the rst ve fours on the right.
ENVIRONMENTAL TECHNOLOGY
Efuents
PO4-P prec.* rate (mmol L1 h1)
1/KP (h)
PO4-P removed when struvite prec. started (mmol L1)
Time of the inexion (min)
Total PO4-P removed (mmol L1)
Time of struvite prec. (min)
Struvite prec. rate (mmol L1 h1)
1/KN (h)
Total NH4-N removed (mmol L1)
Ca prec. rate (mmol L1 h1)
1/KCa (h)
Max.* Ca removed (mmol L1)
Time of Ca diss.* (min)
Ca diss. rate (mmol L1 h1)
1/KdCa (h)
Total Ca removed (mmol L1)
Time of Mg prec. (min)
Max. Mg dissolved (mmol L1)
Mg prec. rate (mmol L1 h1)
1/KMg (h)
Final Mg (mmol L1)
SSW
TASW
CASW
FASW
62 1.2
0.5
4.8 1.2
34.1 0.1
5
10.4 0.3
3.3
36.1 2.6
50.7 0.8
0.4
18.4 1.3
61
13.5 0.2
1.4
8.2 0.5
5
15.4 2.8
2.6 0.1
3.5
4.6 1.4
(14)
where A is the area of the particle and A(O y) the area that can be
covered with discs larger than y. In this calculation y was 0.75.
A. CAPDEVIELLE ET AL.
Figure 4. Distribution of the particles size in number (A) and in volume (B) in the different ASWs.
Final products
pH and concentrations
The amount of magnesia added for precipitation calculated to have a Mg:Ca ratio of about 2 was sufcient to
ENVIRONMENTAL TECHNOLOGY
Final pH
PO4-PStruvite (% of P total)
7.00 0.66
6.81 0.20
6.65 0.15
6.42 0.08
67 6
60 0
76 7
64 5
23.8 1.9
18.0 0.4
22.2 1.7
21.4 1.4
(15)
10
A. CAPDEVIELLE ET AL.
SSW
TASW
CASW
FASW
g L1
0.11 0.04
11
0.88 0.00
91
0.76 0.45 17 11
0.39 0.19
83
Fraction 25100 m
g L1
1.74 0.26
1.13 0.34
2.68 0.80
4.02 0.57
35 3
12 2
61 17
85 1
3.21 0.24 64 2
7.46 0.56 79 2
0.92 0.23 21 6
0.34 0.04 7 2
Discussion
In these investigations, we found that OM had a strong
inuence on the kinetics of the reaction and on the
shape of the crystals formed. The dissolved fraction is
mainly composed of humic substances such as steroids
[24] and ions (all the volatile fatty acids were removed
by the biological treatment [25]). The colloidal fraction
mainly contains proteins. The particular fraction is
mainly composed of carbohydrates and lignocelluloses:
cellulose, hemicelluloses and lignin.[26]
ENVIRONMENTAL TECHNOLOGY
11
Figure 11. XRD patterns of the solids from the different fractions. a,f,i,l: > 25 m; b,j,g,m: 25100 m; c,h,k,n: > 100 m; d: struvite; e:
brushite; o:NaCl.
2kT
1 1
(ri + rj ) + .
Ki,j =
3
ri rj
(16)
b=
(17)
12
A. CAPDEVIELLE ET AL.
Conclusion
The inuence of OM on struvite precipitation in acidied
swine wastewater was negative on the reaction kinetics
but positive on the size of the struvite crystals.
One explanation could be that the DOM prevented
the dissociation of Mg(OH)2 into Mg2+ and OH. The
DOM also modied the shape of the brushite crystals.
The presence of colloidal particles increased the size
of the struvite crystals but slowed down the kinetics
probably because of the viscosity induced by the repulsive force of the colloids.
Table 5. Inuence of OM on struvite crystallization compared to
synthetic media.
SSW
OM
Final pH
Kinetics
MgO dissolution
Brushite crystal growth
Struvite crystal size
Agglomeration
Fraction of Struvite in
nal product
0
0
0
0
0
0
0
FASW
DOM
CASW
DOM +
collodal
TASW
DOM + collodal
particular
++
+++
The particulate OM slowed down all the reaction kinetics. In addition to the effect of DOM on MgO dissolution
steric hindrance linked to the particles could explain this
result. However, the supersaturation was also lower,
which favoured the growth of large crystals of struvite.
The maximum size of single struvite crystals (200 m)
was observed with the presence of particulate OM.
After 24 h, in the acidied swine wastewater, with a
pH increase to 6.8, 90% of the initial P was precipitated
and 60% was precipitated as struvite. Eighty percent of
the solid recovered was in the fraction > 100 m. The
other forms recovered were brushite, ACP, NaCl, KCl
and OM.
Disclosure statement
No potential conict of interest was reported by the authors.
Funding
This work was supported by the French Research National
Agency [grant number ANR2009-ECOT-001401].
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