Environ Chem Lett (2006) 4: 4144

DOI 10.1007/s10311-005-0032-z

ORIGINAL PAPER

F. L. Fu Q. R. Xuan R. M. Chen Y. Xiong

Removal of Cu2+ and dye from wastewater using the heavy metal
precipitant N,N-bis-(dithiocarboxy)piperazine

Received: 27 November 2005 / Accepted: 1 December 2005 / Published online: 19 January 2006


C Springer-Verlag 2005

Abstract We found that a new heavy metal precipitant,
disodium N,N-bis-(dithiocarboxy)piperazine, both precip-
itates Cu2+ ions removes the dye from wastewater. The
precipitation was based on a coordination polymerization
reaction while the removal of the dye could be mainly at-
tributed to an hydrophobic adsorption at pH 7.
Keywords Dye wastewater . Adsorption . Precipitates .
Acid red-73
Introduction
In response to the need of improving these existing
treatment techniques of heavy metal-containing wastew-
ater and increasingly stringent-environmental regulations,
numerous companies have tried to find out more effi-
cient precipitants to remove heavy metals from wastew-
ater (Tandrus 2000). Of these metal precipitants, dithio-
carbamate is the most common. It is often marketed
in two forms, sodium dimethlydithiocarbamate and di-
ethyldithiocarbamate (Matlock et al. 2002). It is noted that
these precipitants only possess single chelating function
to form insoluble complexes with heavy metals, such as
Cu(diethyldithiocarbamate)2 shown in Fig. 1. Recently we
have started to develop a new kind of precipitants with mul-
tiple chelating groups that could form stable coordination
polymer precipitates with heavy metal in wastewater. This
new type of precipitants was referred to as polymerization
precipitants in this paper.
Considering that heavy metal ions are frequently coexis-
tent with dyes in numerous industrial wastewaters, we at-
tempted to investigate the application of the coordination-
polymerization precipitants to the treatment of the com-
F. L. Fu Q. R. Xuan R. M. Chen Y. Xiong (
)
School of Chemistry and Chemical Engineering, Zhongshan
University,
Guangzhou 510275, Peoples Republic of China
e-mail: cesxya@zsu.edu.cn
Tel.: +86-20-84115556
Fax: +86-20-84112245
bination wastewater containing metal ions and dyes. The
original aim of this investigation was to approach the effect
of the coexistent dyes on the removal of heavy metal ions
with the coordination-polymerization precipitants. Unex-
pectedly, in the experiment of precipitating Cu2+ ions from
a combination wastewater containing Cu2+ ions and dye
Acid Red-73 (Fig. 2) with a coordination-polymerization
precipitant, disodium N,N-bis-(dithiocarboxy)piperazine,
(Na2 BDP) (Fig. 3), we found that Na2 BDP not only could
quantitatively precipitate Cu2+ but also could simultane-
ously effectively remove Acid Red-73 dye. It is known that
dyes, like Cu2+ , in rivers and lakes pose a serious envi-
ronment problem. Therefore, this unexpected finding pro-
moted us to further investigate the simultaneous removal of
Cu2+ ions and the dye, specially, the removal mechanism
of the dye and other potential application of this finding.
Experimental
Materials and reagents
The reagents, carbon disulfide, sodium hydroxide, hy-
drochloric acid, sodium diethyldithiocarbamate, ethylene-
diaminetetraacetic disodium (Na2 EDTA), copper sulphate
Fig. 1 Structure of Cu(diethyldithiocarbamate)2
HO
N N N N
NaO 3S
SO3Na
Fig. 2 Chemical structure of Acid Red-73
42
200
Surface charge ( mol/g)
0
3 4 5 6 7 8 9 10
pH
-200
-400
-600
Fig. 3 Chemical structure of N ,N-bis-(dithiocarboxy)piperazine
(BDP)
pentahydrate (CuSO4 5H2 O), hydrazine sulfate, hexam-
ethylenetramine, were purchased from Guangzhou Chem-
icals and of following analytical-grade. Anhydrous piper-
azine (99%) was from Changzhou Shanfeng Chemical
Corporation. The dye of Acid Red-73 (98% purity) was ob-
tained from China Dyestuffs Chemicals and used directly
without further purification. Distilled water was used for all
experimental work. The pH of the solutions was adjusted
using 1.0 mol L1 NaOH and 1.0 mol L1 HCl.
Synthesis of Na2 BDP6H2 O
The Na2 BDP6H2 O was synthesized by the reaction
of piperazine with CS2 and NaOH in dry ethyl ether
and isopropyl alcohol under vigorous stirring over 5 h
(Fabretti et al. 1984). The molar ratio used was as follows:
piperazine:CS2 :NaOH=1:2:2. The crude product was
recrystallized from an aqueous solution containing 50%
methanol.
Analytical apparatus and methods
Elemental analyses were performed on a Vario Elementar.
The residual Cu2+ concentrations of solutions were deter-
mined using flame atomic absorption spectrophotometer
(WFX-1E2) and the reported method (Boca Raton, 1982)
on UV-PC 3101PC spectrophotometer (SHIMASZU,
Japan).
Process of precipitation
Add a definite dose of BDP to 50 mL aqueous solution
containing 50 mg L1 Cu2+ -50 mg L1 Acid Red-73 and
with an initial pH of 5.5, and then agitate for 5 min at a
speed of 85 r min1 . The residual Cu2+ concentrations of
the solutions were analysed after filtration by qualitative
filter paper. All coordination-polymerization experiments
were carried out at 251 C and under normal atmospheric
conditions.
Isothermal adsorption
The isothermal adsorptions of Acid Red-73 on [CuBDP]n
precipitates were conducted in 50-mL flasks. The ex-
11 perimental procedure is as follows: after stiochiometric
dosages of BDP were mixed with 50 mL solution contain-
ing 50 mg L1 Cu2+ and [CuBDP]n precipitates formed,
various concentrations of Acid Red-73 were added in the
resulting suspensions and equilibrated at 301 C for 3 h
on a shaker to ensure the equilibrium. All the adsorption
experiments were carried out at pH 7. After equilibration,
the resulting suspensions were centrifuged and the concen-
trations of Acid Red-73 in the solution were determined
using UV-Vis spectrometer at 509 nm, the maximum ab-
sorption wavelength of the dye. These UV-Vis data were
used to calculate the adsorption capacity qe of the adsorbent
[CuBDP]n precipitates. The adsorption capacity qe given in
milligrams was calculated from the following equation:
(C0 Ce )V
qe = (1)
ms
where C0 and Ce are the initial and final dye concentrations
in solution (mg L1 ), V is the solution volume (L), and
ms is the mass of precipitation (g). In this experiment, the
calculated theoretic mass of [CuBDP]n is 0.01178 g.
Leaching test
Firstly, prepare [CuBDP]n precipitates by the reaction of
BDP and Cu2+ ions in accordance with molar ratio of 1:1
and dry them in a silica gel desiccator. Then, examine the
leaching behaviour of copper ions in [CuBDP]n in water
by monitoring the Cu2+ ion concentrations in the leachant.
To this end, three sets of leaching tests were continuously
performed for 60 days at initial pH 3, 6 and 9, respectively.
In these leaching tests, an initial solutionto-solid ratio of
1000 (50 mL leachant/0.05 g dry [CuBDP]n ) was used.
Determination of the surface charges
for the precipitates
The surface charges for the precipitates were determined
with potentiometric titration method. The potentiomet-
ric titrations were preformed, under N2 atmosphere and
at the temperature of 25 C, with an ionic strength of
0.005 mol L1 KNO3 and a solid-to-liquid ratio of
4.0 g L1 . Standard Crison buffer solutions (pH 4.00, 7.02,
and 9.26) were used to calibrate the electrode. Standard
0.1 mol L1 HNO3 and KOH solutions were used as titrants.
A small amount of HNO3 was then added to protonate a sig-
nificant part of the surface sites, rendering the surface pos-
itive. After 1520 min, the new equilibration pH value was
recorded. The suspension was then titrated by adding small
volumes of a certified volumetric standard of 0.1 mol L1
aqueous NaOH solution, and the pH was recorded as a
function of the volume of titrant added to the suspension.
 43

1.8
Molar ratio of BDP/Cu2+
1.6
No BDP
1.4 0.5:1
Fig. 4 Coordination polymer 0.7:1
1.2

Absorbance
1:1
1.0 1.1:1
Results and discussion 0.8
Coordination polymerization reaction of the BDP 0.6
precipitant and Cu2+ ions
0.4
2+
As BDP was mixed with Cu ions in water, a lot of 0.2
small dark-brown precipitates generated immediately. In 0.0
the process of subsequent 5-min agitation, these small
200 300 400 500 600
precipitates gradually aggregated into some large floccules
and easily subsided from the solution. The Cu2+ ions Wavelength (nm)
were almost removed by the precipitation reaction. The Fig. 5 UV-vis spectral change of Acid Red-73 with the molar ratio
elemental analyses of these precipitates showed C=23.16; of BDP/Cu2+
H=3.26; N=8.48 and S=42.56. The result is rather close
to the theoretical stoichiometry (Cu:BDP=1:1) of the additional experiments showed that single BDP or Cu2+
[CuBDP]n (Liu and Cheng 1995; Fabretti et al. 1984), could not change the colour of Acid Red-73 solution. Ac-
indicating the reaction of BDP and Cu2+ formed an cording to these facts, the removal of Acid Red-73 could
expected coordination polymer as presented in Fig. 4. be primarily contributed to the adsorption of Acid Red-
Batch leaching test is a part of federal and state regu- 73 on [CuBDP]n precipitates, not to the chemical reaction
lations that is used to define toxic hazardousness (Henke between the [CuBDP]n or BDP or Cu2+ ions and Acid
et al. 2000). To examine the copper leachability and sta- Red-73.
bility characteristics of [CuBDP]n coordination polymer, a
batch leaching tests were conducted at different pH values.
Under the condition of pH 3, the accumulated Cu2+ ion Adsorption nature of Acid Red-73 on [CuBDP]n
concentration continuously increased during 60 days and precipitates
reached 1.20 mg L1 after 60 days. However, at pH 6 and
9, the leaching of Cu2+ was observed only at first 10 days, In order to gain a well understanding of the observed de-
and then the accumulated Cu2+ ion concentration basically colourization phenomena, adsorption free energy
G was
remained constant. The Cu2+ ion concentration at the end determined using the following equations (Bhattacharyya
of the 60 days was only about 0.06 mg L1 at pH 6 and and Sharma 2005):
about 0.08 mg L1 at pH 9. Such low leached Cu2+ con-
centrations imply that the [CuBDP]n precipitate was very

qe
S
H
stable in the weak acidic and alkaline environment, that is, log = (2)
at natural condition, and BDP was characterized by fixing Ce 2.303R 2.303RT
the Cu2+ ions for a long term. Therefore, with respective
to the stability of the precipitates, the BDP was a potential
G =
H T
S (3)
new precipitant of Cu2+ ions in wastewater.
where qe is the specific adsorption amount and Ce is dye
Simultaneous removal of Cu 2+
ions and Acid Red-73 concentration at adsorption equilibrium. The
H and
S
were determined from the slope and the intercept of the
As BDP was added in the combination wastewater contain- linear plot of log(qe /Ce ) versus 1/T. By these and Eq. (3),
ing Cu2+ ions and Acid Red-73, apart from almost quanti-
G was calculated to be 7.29 (20 C), 6.94 (30 C) and
tative removal of Cu2+ ions by the coordination polymer- 6.58 (40 C) kJ mol1 , respectively. Generally, the decrease
ization precipitation, the wastewater was unexpectedly ef- in free energy for physical adsorption is between 20 and
fectively decolourized. For a 1:1 molar ratio of BDP/Cu2+ , 0 kJ mol1 , while the decrease for chemical adsorption
only 0.06 mg L1 Cu2+ ions and 15.91 mg L1 Acid Red- is at a range of 80 to 400 kJ mol1 . The above
G
73 was left in the solution, i.e. 99.9% Cu2+ ions and 73% values are all located 0 and 20 kJ mol1 (Yu et al. 2001).
Acid Red-73 were removed. According to this criterion, the adsorption of Acid Red-73
Figure 5 presents UV-Vis spectral change of the Cu2+ -dye on [CuBDP]n precipitates can be considered as a physical
solution with the molar ratio of BDP/Cu. In the figure, no adsorption.
shift of absorption peak was observed although the absorp- To approach the nature of this physical adsorption, the
tion decreased rapidly with increasing of BDP. Moreover, change in adsorption over pH 311 was determined. As
44

240 Their correlation coefficients (R2 ) of Langmuir (Ce /qe

versus Ce ) and logarithmic Freundlich plots for the re-
Acid Red-73 moval of Acid Red-73 with the precipitates were 0.9537
Adsorbed amount (mg/g)

220 methylene blue and 0.9964, respectively, implying the Freundlich model
was more suitable than Langmuir model for the describing
200 the adsorption equilibrium. The Freundlich exponent n is
2.17, locating between 1 and 10. This result indicated the
adsorption was a favourable process.
180

160 Conclusion

140
4 6 8 10
Initial pH
Fig. 6 Effect of initial pH on adsorption of the dyes (60 mg/L) on
[CuBDP]
Fig. 7 Potentiometric titration curve of Cu[BDP]n precipitates
seen from Fig. 6, the precipitates adsorbed not only an-
ionic dye Acid Red-73 but also cationic dye methylene
blue in the whole pH range. This fact implied that the ad-
sorption was dependent on not only the surface charge of
the precipitate but also hydrophobic interaction. Moreover,
it was known from Fig. 7 that the pH of the point of zero
charge (pHpzc ) of the precipitate is 5.7, therefore, the pre-
cipitate for the experimental pH 7 was characterized with
negative charges, and however, its adsorption amount for
anionic Acid Red-73 is much higher than for cationic MB
as shown in Fig. 6. This fact suggests that the main factors
controlling the adsorption were hydrophobic interaction at
pH 7.
In order to approach the thermodynamic performance of
the adsorption, isothermal adsorption experiment for Acid
Red-73 on [CuBDP]n was conducted and these experimen-
tal data were analysed with the following linearised Lang-
muir and Freundlich isotherms:
Ce 1 Ce
= +
qe Q0b Q0
1 mercial reagents for heavy metal removal from water with new
log(qe ) = log K f + log(Ce )
n insights for future chelate designs. J Hazard Mater B92:129
where Ce is the equilibrium concentration, qe is the ad-
sorbed amount, Q0 and b are Langmuir constants. Kf is the
Freundlich constant and n is the Freundlich exponent.
The above results showed BDP precipitant could not only
effectively precipitate Cu2+ ions and fix them for long
time, but also simultaneously remove dyes. The removal
of the former was by the coordination polymerization re-
action while the removal of latter was with the adsorption
of [CuBDP]n precipitates. The application of solid waste to
the removal of colour is considerably attractive (Blackburn
2004), and the resulting [CuBDP]n precipitates as waste
solids in the treatment process of Cu2+ ion-containing
wastewater which is perhaps used as cheap and effective
adsorbent for other dye wastewater, including anionic and
cationic dyes. However, prior to its practical application,
a lot of investigations, such as more dyes and metals, are
needed.
Acknowledgements This work was supported by Nature Science
Foundations of China (50578163 and 20277046) and Guangdong
Province (04009713).
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