Chemical Engineering Journal 185186 (2012) 219225

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Chemical Engineering Journal
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Efcient and controllable phosphate removal on hydrocalumite by multi-step
treatment based on pH-dependent precipitation
Ji Zhi Zhou

, Linlin Feng, Jun Zhao, Jianyong Liu, Qiang Liu, Jia Zhang, Guangren Qian
School of Environmental and Chemical Engineering, Shanghai University, No.333 Nanchen Rd., Shanghai 200444, PR China
a r t i c l e i n f o
Article history:
Received 7 December 2011
Received in revised form14 January 2012
Accepted 17 January 2012
Keywords:
Ca
2
Al-Cl-LDH
Phosphate
Wastewater
PHREEQC
Precipitation
a b s t r a c t
The phosphate removal on hydrocalumite (Ca
2
Al-Cl-layered double hydroxide, Ca
2
Al-Cl-LDH) was eval-
uated by PHREEQC program, which indicated that a pH-dependent dissolutionreprecipitation process
was responsible for the phosphate elimination. The evaluation results also suppose that in the solu-
tion with high phosphate concentration, the formation of CaHPO
4
2H
2
O (DCPD) and AlPO
4
at pH< 7.0
attributed to more phosphate removed than that in the conventional treatment where only hydroxya-
patite (HAP) was precipitated. This hypothesis was conrmed by XRD characterization and the removal
efciency of phosphate in batch experiments. Accordingly, the multi-step treatment process (MST) was
conducted for the removal phosphate in real P-containing wastewater, in which DCPD and AlPO
4
were
formed at low pH and HAP at high pH. This resulted in the increasing amount of phosphate removal to
9.26 mmol/g Ca
2
Al-Cl-LDH due to the high consuming efciency of Ca and Al in the whole process. The
other benet of MST was 12.7% of mass reduction of the as-obtained sludge, compared to the conven-
tional one-step treatment. Our work proposed a potential strategy for the improvement of phosphate
removal by Ca
2
Al-Cl-LDH.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Removal of phosphate in wastewater from industrial, agricul-
tural and household activities has attracted much attention as
phosphate is responsible for eutrophication of rivers, lakes and
bays and damage of the aquatic eco-system[1,2]. For this purpose,
many strategies have been developed to eliminate phosphate in
the efuent, such as bio-treatment with granular activated sludge
[3] and physical/chemical treatment with clay materials [46] and
modiedones [79], activecarbon[10], oxides/hydroxides [1113],
La-modied silica [14,15]. Among these treatments, chemical pre-
cipitation with iron, aluminum, and calciumsalts is a widely used
method for the treatment of phosphorus [16].
Based on the great concern about the effective removal,
Cl intercalated Ca
2
Al-layered double hydroxide (Ca
2
Al-Cl-LDH,
Ca
4
Al
2
(OH)
12
Cl
2
4H
2
O), amember of anionic clays, exhibitedahigh
efciency for phosphate removal from wastewater [1719]. Our
group has found that Ca
2
Al-Cl-LDH removed phosphate through
the dissolutionreprecipitation mechanism [19]. In this process,
phosphate precipitates with Ca
2+
dissolved from LDH to form
insoluble hydroxyapatite (Ca
5
(PO
4
)
3
OH, HAP) due to the much
low solubility product of HAP (Ksp=210
58
, [20]). In particular,

Corresponding author. Tel.: +86 21 66137746; fax: +86 21 66137758.

E-mail address: jizhi.zhou@shu.edu.cn (J.Z. Zhou).
the higher removal amount of phosphate, about 135mg P/g, was
observed at lower initial pH (5.0). Despite, the treatment of phos-
phate on Ca
2
Al-Cl-LDH is limited by the following issues: (1) the
increase of pH up to 12.0 due to OH

releasing from LDH; (2) low

consuming efciency of Ca in P removal as 1.67 of the molar Ca/P in
HAP; (3) little contribution of Al(OH)
3
to the adsorption of P due to
the conversion of Al(OH)
3
to soluble Al(OH)
n
(n 3)
(n>3) at high
pH [11].
On the other hand, phosphate and calcium can be precipitated
in various insoluble species apart from HAP. Under different con-
ditions, such as temperature, the level of supersaturation, pH, and
initial concentration of reagents, the following Ca-phosphate pre-
cipitates are formed [21,22]: Hydroxyapatite (HAP, Ca
5
(PO
4
)
3
OH),
tricalcium phosphate (-TCP, Ca
3
(PO
4
)
2
), octacalcium phosphate
(OCP, Ca
8
H
2
(PO
4
)
6
5H
2
O), monetite (DCPA, CaHPO
4
), and brushite
(DCPD, CaHPO
4
2H
2
O), tetracalciumphosphate (TTCP, Ca
4
(PO
4
)
2
O)
and amorphous calcium phosphate (amorphous Ca
9
(PO
4
)
6
xH
2
O,
ACP). Apparently, both DCPA and DCPD have the lowest Ca/P, giv-
ingthehighest Ca efciencyinthePremoval. Moreover, DCPDis the
predominant precipitate withthe pHbelow7.0 inaqueous solution
[2224].
Such a pH value allows Al to exist predominantly in the form
of Al(OH)
3
with a small portion of Al
3+
[11] when Ca
2
Al-Cl-LDH is
used as Ca source for the phosphate precipitation. In the presence
of Al(OH)
3
and Al
3+
, the P removal was attributed to the adsorption
on Al(OH)
3
and the precipitation with Al
3+
in the form of AlPO
4
,
1385-8947/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.086
220 J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225
Table 1
Potential minerals in the evaluation by PHREEQC model.
Ca/P (molar ratio) Compound Formula LogKsp (25

C) Reference
1 Brushite (DCPD) CaHPO
4
2H
2
O 6.59 [3]
1 Monetite (DCPA) CaHPO
4
6.9 [39]
1.33 Octacalciumphosphate (OCP) Ca
4
H(PO
4
)
3
2.5H
2
O 48.3 [39]
1.5 Tricalciumphosphate (TCP) Ca
3
(PO
4
)
2
32.69 [36]
1.67 Hydroxyapatite (HAP) Ca5(PO
4
)
3
OH 58.52 [20]
Gibbsite Al(OH)
3
32.34 [25]
AluminumPhosphate AlPO
4
18.24 [25]
Hydrocalumite Ca
4
Al
2
(OH)
12
Cl
2
4H
2
O 27.1 [29,30]
respectively [25,26]. As a result, the P removal on Ca
2
Al-Cl-LDH
would be improved by the formation of DCPD and AlPO
4
and the
adsorption of Al(OH)
3
at lowpH.
Herein, the objectives of this study were to: (1) evaluate the
optimal conditions of DCPDformation by PHREEQC 2.12; (2) inves-
tigate the phosphate removal behavior on Ca
2
Al-Cl-LDH at high
phosphate concentration, compared to that on CaCl
2
and AlCl
3
;
(3) develop the DCPD formation strategy in the treatment of real
phosphate-containing wastewater by Ca
2
Al-Cl-LDH. We foundthat
the multi-step controlling of DCPD crystallization is a facile and
cost-effective strategy for the improvement of phosphate removal
with less sludge production.
2. Materials and method
2.1. Materials
Ca
2
Al-Cl-LDH was prepared with a co-precipitation method
as reported elsewhere [27]. Typically, the salt mixture solution
(50ml) composed of 50mmol of CaCl
2
and 25mmol of AlCl
3
6H
2
O
was quickly added to the alkaline solution (100ml) containing
150mmol of NaOH under vigorous stirring for 1h with owing
N
2
stream. The suspension was aged at 25

C for 18h under stir-

ring. The precipitate was then collected via ltration, thoroughly
washedwithdeionizedwater anddriedat 100

Cinanoven. The as-

prepared sample was pressed and crushed to the mesh size of 100
prior to further experiment. The sample was identied by the ICP,
XRD and C/H/O element analyses to be a pure Ca
2
Al-Cl-LDH with
the approximate formula of Ca
1.8
Al(OH)
5.6
Cl
0.95
(CO
3
)
0.025
2.5H
2
O
(M.W. =275g/mol), with XRD pattern being consistent to that
reported elsewhere (JCPDS No 78-1219) with the d
003
-spacing of
0.776nm[27].
2.2. PHREEQC programModeling
PHREEQC (version 2.12.5), a low-temperature aqueous geo-
chemical calculation computer program, developed by the US
Geology Survey can be applied in saturation-index (SI) calcula-
tionand speciationanalysis for modeling precipitationdissolution
chemical equilibrium[28]. Before the calculation, the Ca
2
Al-Cl-LDH
thermodynamic data with logKsp=27.1, G
o
r
= 154.68kJ/mol
[29,30] was input into PHREEQC database.
In current simulation of phosphate removal, the initial param-
eters were: phosphate concentration ranging from 2mg/L to
1000mg/L (0.06532.3mmol/L); equilibriumpH value from2.0 to
14.0; the temperature at 25

Cinall tests; and Ca

2
Al-Cl-LDHdosage
of 1g/L. Thecompiledprograms werecalculatedwiththeWATEQ4F
database [28]. Potential minerals with corresponding solubility
product (Ksp) in PHREEQC database were shown in Table 1. The
output data of the activities, the free ionic activities product and
saturation-indexes of every species as well as the solution ionic
strength were used to evaluate the potential precipitations in the
phosphate removal process.
2.3. Batch experiments
The experimental removal of phosphate was performed in
a 150-ml sealed conical ask with 100ml of KH
2
PO
4
solution
([P] =1000mg/L =32.3mmol/L) and 0.10g of dosage of Ca
2
Al-Cl-
LDH. The removal process was carried out at 251

C for 48h
shaking in a water-bath. By dripping diluted HCl or NaOH solution
(0.01 and 0.001mmol/L), the solution pH was kept at 5.0, 7.0 and
11.00.1, respectively, monitored by the pH sensor with0.01
of precision. For comparison, CaCl
2
and AlCl
3
6H
2
O were used to
remove phosphate in the similar way where the molar dosage of
metal was as much as that of corresponding one in 0.10g of LDH.
After removal, the suspension was ltered by 0.22m micro-
pore membrane. The resultant solid was collected after water
washing and drying at 100

C in an oven for further charac-

terization. The composition of the separated solution was also
determined. All experiments were carried out in triplicate with the
reproducibility within 5%.
2.4. Multi-step treatment
Amulti-steptreatment (MST) of phosphate-containingwastew-
ater was performed on Ca
2
Al-Cl-LDH, which was based on DCPD
precipitation. Briey, as illustrated in Fig. 1, 1.5g/L of Ca
2
Al-Cl-LDH
was added in the rst step treatment (Step-1) to increase the nal
pH to 4.05.0 as the dissolution of Ca
2
Al-Cl-LDH. After ltering,
the separated solution was ready for next step treatment (Step-2)
where another 1.5g/L of Ca
2
Al-Cl-LDH was added and the nal pH
was increased to 5.07.0. In the last step (Step-3), the pHwas up to
11.0 or more by NaOH solution.
Similar to that in the batch experiment, the phosphate removals
in both Step-1 and Step-2 were performed in a 150-ml sealed
conical ask under stirring for 24h. Whereas, the last step for phos-
phate removal was carried out for 0.5h. The solid after each step
Fig. 1. Schematic of the multi-step treatment for P removal fromreal wastewater.
J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225 221
treatment was collected by ltering while the solution was sep-
arated for next step treatment. For comparison, the conventional
treatment of the wastewater [31] was carriedout inthe similar way
where 3.0g/L of LDH and NaOH solution were added together into
100ml of wastewater.
2.5. Chemical and physical characterization
The pH value was monitored with an Elico digital pH meter
(Model LI-120) using a combined glass electrode (Model CL
51). The phosphate concentration was determined in a UNICO
UV-spectrophotometer (4802UV/VIS), at 700nm, following molyb-
denum orchid colorimetric method (GB11893-89) [32]. The metal
concentrations insolutionweredeterminedbyInductivelyCoupled
Plasma-Atom Emission Spectrometer (ICP-AES, Prodidy, Leeman
Co.). The C, H, and Ocomponents in LDHwere detected by Element
Analysis (EA3000, Leeman Co.).
Powder X-ray diffraction (XRD) was carried out on a D\MAX-
2200 X-ray diffractometer (Rigaku Co.) with Cu K radiation
(=0.15406nm) at a scanning rate of 8

/min from5

to 80

(2).
3. Results and discussions
3.1. PHREEQC modeling evaluation
3.1.1. Phosphate precipitates at various initial concentrations
The species of potential precipitates was evaluated by PHREEQC
model as shown in Fig. 2, in which the dissolution of LDH was
revealed as no LDH remaining in the solid phase with all Al precip-
itated in gibbsite (Al(OH)
3
). AlPO
4
and various CaP solid species
were formed at different initial [P] in some cases.
Fig. 2A illustrates that with the increase of initial [P], most gibb-
site was converted to AlPO
4
at initial [P] >4mmol/L in the case of
pH 5.0. The amount of Al in AlPO
4
was about 3.6mmol/L, same as
the theoretical Al content in Ca
2
Al-Cl-LDH (1.0g/L of LDH dosage).
It was found that the dissolved Ca
2+
precipitated P to form DCPD
at initial [P] >14mmol/L. The similar result was obtained in the
case of pH 7.0 where the conversion of gibbsite occurred at initial
[P] from 10mmol/L to 14mmol/L and DCPD was formed at initial
[P] >23mmol/L (Fig. 2B). In particular, TCP was formed with initial
[P] increasingwhereas transformedcompletelytoDCPDafter initial
[P] of 27mmol/L. Obviously, high initial P concentration improved
the DCPD formation at pH7.0. Different from that at lower pH,
the predominant P precipitate was HAP at higher pH. In Fig. 2C,
only gibbsite and HAP were obtained at pH 11.0 regardless of the
initial [P]. The amount of Al in gibbsite was only 3.043.07mmol/g
that is less than 3.63mmol/g of the theoretical Al content in Ca
2
Al-
Cl-LDH. This is attributed to the high amount of OH

that converts
some Al(OH)
3
to Al(OH)
n
(n3)
.
According to the diversity of precipitates above, the phosphate
removal efciency at various initial [P] was estimated and shown
in Fig. 2D. The HAP formation resulted in the constant P removal
amount up to 4.28mmol/g at pH 11.0. In comparison, the phos-
phate removal efciency at pH 7.0 was considerably increased at
initial [P] >10.5mmol/L due to the formationof AlPO
4
and TCP. Fur-
thermore, more phosphate was removedat initial [P] >24.5mmol/L
due to the conversion of TCP to DCPD. The effect of DCPD forma-
tion was also observed in the case of pH 5.0 where the P removal
amount was increased gradually at initial [P] >14.5mmol/L. There-
fore, it is supposed that the formation of DCPD can result in the
higher P removal amount, especially at high initial [P].
3.1.2. Effect of pH
Besides the initial [P], the pHhas a signicant effect onthe phos-
phate removal efciency as well. Fig. 3 shows the estimation result
of P removal at various pHs but a xed initial [P] of 32.3mmol/L.
32 28 24 20 16 12 8 4 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Gibbsite
AlPO
4
DCPD
P
o
t
e
n
t
i
a
l

m
i
n
e
r
a
l
s

(
m
m
o
l
/
L
)
P concentration (mmol/L)
A pH=5.0
32 28 24 20 16 12 8 4 0
0
1
2
3
4
5
6
7
P
o
t
e
n
t
i
a
l

m
i
n
e
r
a
l
s

(
m
m
o
l
/
L
)
Gibbsite
AlPO
4
DCPD
TCP
P concentration (mmol/L)
B pH=7.0
32 28 24 20 16 12 8 4 0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
P
o
t
e
n
t
i
a
l

m
i
n
e
r
a
l
s

(
m
m
o
l
/
L
)
Gibbsite
HAP
P concentration (mmol/L)
C pH=11.0
32 28 24 20 16 12 8 4 0
0
2
4
6
8
10
12

R
e
m
o
v
a
l

e
f
f
i
c
i
e
n
c
y

(
m
m
o
l
/
g
)
P concentration (mmol/L)
pH=5.0
pH=7.0
pH=11.0
D
Fig. 2. Amount of potential precipitates by PHREEQC evaluation at xed pH 5.0 (A),
7.0 (B) and 11.0 (C) as well as the total phosphate removal amount (D) on Ca
2
Al-Cl-
LDH with various initial phosphate concentrations.
222 J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225
14 12 10 8 6 4 2
0
2
4
6
8
10
12
pH
AlPO
4
DCPD
HAP
TCP
Gibbsite
0
2
4
6
8
10
P
o
t
e
n
t
i
a
l

m
i
n
e
r
a
l
s

(
m
m
o
l
/
L
)
P

r
e
m
o
v
a
l

e
f
f
i
c
i
e
n
c
y

(
m
m
o
l
/
L
)
P removal rate
[P] = 32.3 mmol/L
Fig. 3. Potential minerals and phosphate removal amount on Ca
2
Al-Cl-LDH evalu-
ated by PHREEQC at the pH range of 2.014.0 with initial [P] =32.3mmol/L.
At pH from 2.5mmol/g to 7.0, 3.6mmol/g of AlPO
4
was formed,
indicating that most of Al in LDH contributed to P removal. In con-
trast, most AlPO
4
was converted to gibbsite at pH 7.07.5 while
gibbsite gradually dissolved as Al(OH)
n
(n3)
formed at pH>10.0.
This suggests that the removal of P with Al was more available at
pH<7.0.
Moreover, there were DCPD, TCP and HAP precipitated predom-
inantly at pH 4.57.5, 7.09.0, and 8.514, respectively. Excluding
the P in AlPO
4
, the formation of DCPDresulted in about 7.0mmol/g
of P (=10.63.6mmol/g) removed at pH 6.57.0, 1.521.64 times
higher than those in cases of TCP and HAP precipitation. It is indi-
catedthat more P canbe removedat pH<7.0whenDCPDandAlPO
4
were formed.
3.1.3. Response surface curves
Since the species of precipitates depended on pH and ini-
tial phosphate concentration, the reciprocal effect of these two
factors for phosphate removal efciency over Ca
2
Al-Cl-LDH was
estimated by response surface curves. As shown in Fig. 4, at ini-
tial [P] >160mg/L and pH ranging from 5.0 to 7.0, the P removal
efciency was higher than that under other conditions. This is
attributed to the formation of AlPO
4
, DCPD and TCP. On the con-
trary, at a lower phosphate concentration (2160mg/L), high pH
(above 9.0) removed approximate 100% of P due to HAP formation.
The evaluation result indicates that for P removal in wastewater
with high P concentration, the formation of DCPD and AlPO
4
at
pH<7.0 is a more efcient way than that of HAP.
3.2. Phosphate removal in batch experiment
3.2.1. Species of precipitates under various pHs
The experimental P removal was carried out in the batch test.
Fig. 5 shows XRD patterns of the product after the phosphate
removal by Ca
2
Al-Cl-LDH, CaCl
2
, AlCl
3
, and the mixture of CaCl
2
and AlCl
3
(Ca/Al mixture) with different pHs. In the case of Ca
2
Al-
Cl-LDH, Fig. 5Aexhibits that complete dissolutionof LDHregardless
of various pH values. The DCPD (JCPDS No 72-0713) was identied
with low reections of gibbsite (JCPDS No 74-1775) at pH 5.0 and
7.0. This is consistent to the result in Fig. 3 under similar condi-
tions. Moreover, HAP (JCPDS No 86-0740) was observed at pH 7.0,
indicating partial DCPD were probably transformed to HAP. At pH
11.0, a board HAP peak with gibbsite was reected in XRD pattern.
Similarly, in the presence of Ca
2+
only, Fig. 5B displays that DCPD
and HAP was observed at pH 7.0 while only HAP at pH 11.0. This
indicates soluble Ca
2+
was responsible for the P removal at both pH
7.0 and 11.0 in the case of LDH. However, there was no any precip-
itate at pH 5.0. The observation suggests that the P removal at pH
5.0 was not mainly attributed to the DCPD precipitate although its
XRDpattern indexed in the case of LDH. In addition, the patterns of
OCP (JCPDS No 79-0423) was identied which was contributed to
the predominant HPO
4
2
in the solution at pH 7.0 [33].
As shown in Fig. 2, the conversion of Al(OH)
3
to AlPO
4
was con-
sidered at lowpHdue to the dissolution of Al(OH)
3
. Fig. 5C displays
the broad peak at 2535

(2) in the XRDpatterns of both products

at pH 5.0 and pH 7.0, indicating a poor crystallized AlPO
4
formed
when Al
3+
was added in the phosphate solution [25]. Due to less
DCPD formed at pH 5.0 (Fig. 5B), it is demonstrated that AlPO
4
contributed to the P removal predominantly in the case of LDH.
Accordingly, poor crystallized AlPO
4
was also suggested in Fig. 5A
as the similar broad peak at 2535

(2) at pH 5.0. Furthermore,

the formation of soluble Al(OH)
n
(n 3)
resulted in the dissolution
of Al(OH)
3
so that there was no product obtained at pH 11.0 in the
case of AlCl
3
, demonstrating that most P over Ca
2
Al-Cl-LDH was
removed in HAP like the situation in previous work [19], which is
in good agreement to the result in Fig. 3.
As shown in Fig. 5D, the effect of Ca
2+
combined with Al
3+
resulted in amorphous AlPO
4
at pH 5.0, DCPD crystal and amor-
phous AlPO
4
(aboardpeakat 2535

(2)) at pH7.0, andHAPcrystal

at pH 11.0, respectively. This observation was different from the
result in the case of Ca
2
Al-Cl-LDH(Fig. 5A) at pH5.0 and 7.0. It sup-
poses that the P removal process on LDH was not similar to that in
the presence of free Ca
2+
and Al
3+
.
3.2.2. Practical P removal process
Fig. 6 shows phosphate removal percentage at various pHs in
the batch experiment. The sum of P removal percentages in cases
Fig. 4. Response surface curves of phosphate removal efciency versus pH(2.014.0) and phosphate concentration(21000mg/L) over Ca
2
Al-Cl-LDHby PHREEQCevaluation.
J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225 223
Fig. 5. XRD pattern of the products after the phosphate removal with initial [P] =32.3mmol/L at pH 5.0, 7.0 and 11.0 on (A) Ca
2
Al-Cl-LDH, (B) CaCl
2
, (C) AlCl
3
and (D) Ca/Al
mixture.
0
5
10
15
20
25
30
35
40
0
1
.
2
6
AlCl
3
1
3
.
6
3
1
.
1
1
6
.
7
1
.
2
6
1
4
.
1
1
1
.
1
1
5
.
9
1
7
.
1
1
7
.
3
1
6
.
7
pH 5.0
pH 7.0
pH 11.0
Ca/Al mixture CaCl
2
R
e
m
o
v
a
l

(
%
)
pH in solution
Ca
2
Al-Cl-LDH
1
9
.
2
Fig. 6. Removal percentage of phosphate at various pHs in cases of Ca
2
Al-Cl-LDH,
CaCl
2
, AlCl
3
and Ca/Al mixture.
of CaCl
2
andAlCl
3
was closetothePremoval percentageinthepres-
ence of both CaCl
2
and AlCl
3
. This is consistent to the XRD result in
Fig. 5, which indicates that the P removal was contributed to the
precipitation of Ca
2+
and Al
3+
with P. Moreover, the P removal per-
centage in the case of Ca/Al mixture was also similar to estimated
values in PHREEQC model at pH 7.0 and 9.0 (Fig. 3) where the P
removal percentage was 35.6% and 15.4%, respectively. It is noted
that at pH 5.0, the theoretic removal percentage was 24.1%, higher
than that of 13.6% in the case of Ca/Al mixture. This observation is
attributed to the absence of DCPD in the present case as no DCPD
pattern in XRD result in Fig. 5D.
OnCa
2
Al-Cl-LDH, 19.2%of total Pwas removedat pH5.0, slightly
higher than that in the case of Ca/Al mixture. It is due to the forma-
tion of DCPD on Ca
2
Al-Cl-LDH as shown in Fig. 5A. At pH 7.0, the P
removal percentage was 17.3%, about two times lower than that in
the case of Ca/Al mixture. Such difference in P removal percentage
is contributed to the conversion of DCPD to HAP and the forma-
tion of Al(OH)
3
as the XRD pattern of HAP and Al(OH)
3
identied
in Fig. 5A. Moreover, the formation of HAP at pH 11.0 was respon-
sible for the P removal as the 16.7% of P removal percentage on the
Ca
2
Al-Cl-LDH, same as that in the case of Ca/Al mixture. Therefore,
224 J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225
Table 2
Composition of electroplating efuent after two different removal processes.
(mmol/L) pH [P] [Zn] [Ca] [Al]
Blank 2.47 27.8 17.1 0.800 0.357
Step-1 4.56 18.2 7.31 10.6 0.203
Step-2 5.66 5.78 0 13.3 0.166
Step-3 11.58 0.00314 0 3.82 0.0178
One-step 11.21 5.84 0 0.0548 3.21
it is suggested that the P removal efciency on Ca
2
Al-Cl-LDH was
much lower at high pH, compared to that in the presence of free
Ca
2+
and Al
3+
. The high P removal amount was probably obtained
at lowpH on Ca
2
Al-Cl-LDH.
3.3. Multi-step treatment (MST)
3.3.1. Controllable phosphate removal
To improve the P removal, MST was performed in the raw
wastewater with low initial pH. The pH and aqueous composition
are listed in Table 2. It is noted that 17.1mmol/L of soluble Zn was
detected in the wastewater apart fromP.
Table 2 also shows the nal pHandcompositionof solutionafter
treatment. In the Step-1 of MST, the nal pH was increased from
2.47 to 4.56. It was attributed to the complete dissolution of LDH
that resulted in the Ca increasing amount of 9.80mmol/L in the
nal solution (10.60.800mmol/L, Table 2), close to 9.82mmol/L
of total theoretical Ca in 1.5g/L of LDH. This also reveals that the
released Ca
2+
has less effect on the P reduction from27.8mmol/L to
18.2mmol/L. It is consistent to the results in Fig. 3 as well as Fig. 5B.
In comparison, the lowaqueous Al concentration in the nal solu-
tion indicates that the LDH dissolution at low pH did not result in
the releasing of soluble Al. As the formationof AlPO
4
was suggested
inFig. 3at pH<7.0, theinsolubleAl was probablyresponsiblefor the
P removal with Al. Besides, the concentration of Zn was decreased
from 17.1mmol/L to 7.31mmol/L, indicating that 9.79mmol/L of
Zn reduction is attributed to the precipitation of Zn
3
(PO
4
)
2
4H
2
O
withP [3436]. Therefore, the 9.60mmol/L of P reductionwas com-
posed of 6.53mmol/L of P removed by Zn
3
(PO
4
)
2
4H
2
O formation
and 3.07mmol/L of P uptake in AlPO
4
.
In the Step-2, the pH increased from 4.56 to 5.66 due to the
complete dissolution of Ca
2
Al-Cl-LDH. However, the Ca increas-
ing amount was only 2.70mmol/L (13.310.6mmol/L, Table 2) in
nal solution, indicating that 7.12mmol/L of Ca was precipitated
(9.822.70mmol/L, Table 2). This suggests that the precipitation of
Ca was attributed to 7.12mmol/L of the P removal to form DCPD
at pH 5.66 as DCPD formation in the precipitate at pH 5.07.5
(Fig. 3). This observationillustrates that 57.1%of P removedinStep-
2 was contributed to the Ca in LDH. Similar to that in Step-1, the
removal of Pwas alsorelative toZndue to7.31mmol/L of Znprecip-
itated. The low aqueous Al concentration in the nal solution was
also shown in Table 2, as AlPO
4
was formed (Fig. 3A). Therefore,
12.4mmol/L of P reduction is attributed to the combined effect of
Ca, Zn and Al.
In the last step, pH increased to 11.58 with NaOH addition.
Simultaneously, the Ca concentration decreased from13.3mmol/L
to 3.82mmol/L with the P removal amount of 5.78mmol/L. Note
that the molar ratio of removed Ca to P was 1.64, close to 1.67
of the theoretical Ca/P ratio in HAP. It indicates Ca reduction was
responsible for the P removal as the HAP precipitation was pre-
dominant in the basic solution (Fig. 3). After MST, the residual [P]
in the solution was 0.00314mmol/L, lower than 0.0161mmol/L of
P in its discharge limitation standard [37].
In contrast, the remaining [P] was 5.84mmol/L in nal solution
at pH 11.21 in the case of one-step treatment. This is contributed
to the increase of Ca/P in HAP that was formed at higher pH with
Fig. 7. XRDpattern of products after the phosphate removal fromthe real P-bearing
wastewater on Ca
2
Al-Cl-LDH by two different treatment processes.
the dissolution of LDH (Fig. 3). In addition, as the quick formation
of HAP under the high pH and [P], partial Ca
2
Al-Cl-LDH particle
was gradually wrapped and its dissolution was inhibited [19]. This
incomplete dissolution of LDH also resulted in the high [P] resid-
ual. On the other hand, [Al] in the nal solution was much higher
than that in the multi-step treatment. The high residual [Al] in the
one-step treatment was attributed to more total Al added in the
system. There was 10.9mmol/L of Al in one-step treatment while
only 0.166mmol/L of Al left after Step 2 in multi-step treatment
(Table 2). As the equilibriumof Al(OH)
3
and Al(OH)
n
(n3)
at basic
solution[19], moreAl inthesystemresultedinmoreAl convertedto
soluble Al(OH)
n
(n 3)
. This indicates less P was removed at current
pH in the one-step treatment.
The other benet of MST was the reduction of sludge mass after
treatment. In MST, the mass of sludge was 12.7% lower than that in
one-step treatment.
3.3.2. Precipitates in MST process
The precipitations of P removal in MST were conrmed by
XRD. As shown in Fig. 7, Zn
3
(PO
4
)
2
4H
2
O (JCPDS No 37-0465) was
identied in the precipitate at Step-1, which demonstrates the P
removal with Zn
2+
. Due to the poor crystal of AlPO
4
, it was not
observed in XRDpattern. In the Step-2, the formation of DCPDwith
a little gibbsite was identied in XRD pattern. Moreover, partial
P was removed in CaZn
2
(PO
4
)
2
2H
2
O (JCPDS No 71-2275), which
was observed by Nriagu [38]. These indicate that P was removed
in precipitates of DCPD and CaZn
2
(PO
4
)
2
2H
2
O and adsorption
of gibbsite, respectively. Take into account hydration constant of
H
3
PO
4
(logK
a2
=7.20) [40], the species of phosphate adsorbed on
gibbsite may be predominately H
2
PO
4

at pH=5.66. The poor crys-

tal of AlPO
4
was not still observed. In the two steps above, 79.2% of
P has been removed. In the last step, HAP was the only detectable
phase, which is consistent to previous result [19]. In comparison,
part of Ca
2
Al-Cl-LDH was still observable in XRD pattern after
J.Z. Zhou et al. / Chemical Engineering Journal 185186 (2012) 219225 225
one-step treatment, indicating lowP removal efciency at basic pH
and high phosphate concentration by dissolutionreprecipitation
in the case of Ca
2
Al-Cl-LDH.
4. Conclusions
We investigatedphosphateremoval process onCa
2
Al-Cl-LDHby
PHREEQC modeling as well as the batch experiment. The PHREEQC
modeling assessment indicated that in a wastewater with high P
concentration, the formation of DCPD and AlPO
4
at pH<7.0 was
a more efcient way for P removal, compared to the formation
of HAP. The higher P removal amount was obtained at low pH
(5.07.0) due to the formation of DCPD and AlPO
4
. This evaluated
result was conrmed by batch experiments.
Accordingly, a multi-step treatment was performed for the P
removal from a real phosphate-containing wastewater by Ca
2
Al-
Cl-LDH. The results revealed that controlling DCPD and AlPO
4
formation at low pH improved the efciency of P removal as well
as reduced the mass of as-obtained sludge, compared to one-step
treatment with the same dosage of Ca
2
Al-Cl-LDH.
Acknowledgements
This project is nancially supported by National special
S&T project on treatment and control of water pollution No.
2008ZX07421-002, No. 2009ZX07106-01, National Nature Science
Foundation of China No. 20677037/B07034, No. 20877053/B0703,
No. 20907029/B0703 and Shanghai Leading Academic Discipline
Project No. S30109. This work is also supported by the State Schol-
arship Fund (No. 2009689027) by China Scholarship Council and
Shanghai University Innovative Foundation for Higher Degree Stu-
dents. We also appreciate the technical support fromInstrumental
Analysis & Research Center of Shanghai University.
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