Wat. Res. Vol. 35, No. 2, pp.

496–500, 2001
# 2000 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(00)00279-7 0043-1354/00/$ - see front matter

ADSORPTION MECHANISM OF HEXAVALENT CHROMIUM

BY REDOX WITHIN CONDENSED-TANNIN GEL
YOSHIO NAKANO*M, KENJI TAKESHITA and TOSHIRO TSUTSUMI
Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta,
Midori-ku, Yokohama 226-8502, Japan

(First received 27 August 1999; accepted in revised form 12 May 2000)

Abstract}We have proposed a new recovery system of hexavalent chromium Cr(VI) that is of great
toxicity utilizing condensed-tannin gels derived from a natural polymer with many polyhydroxyphenyl
groups. The adsorption mechanism of Cr(VI) to the tannin molecules was clarified. The adsorption
mechanism consists of four reaction steps; the esterification of chromate with tannin molecules, the
reduction of Cr(VI) to trivalent chromium Cr(III), the formation of carboxyl group by the oxidation of
tannin molecules and the ion exchange of the reduced Cr(III) with the carboxyl and hydroxyl groups. It
was found in this recovery system that a large amount of proton was consumed accompanied with the
reduction of Cr(VI) so that the acidic solution containing Cr(VI) was transferred automatically to neutral
one by choosing an appropriate initial pH. The carboxyl group which was created by the oxidation of
tannin molecules parallel to the reduction of Cr(VI) to Cr(III) contributed to an increase in the ion-
exchange sites of the reduced Cr(III). The maximum adsorption capacity of Cr(VI) reached 287 mg Cr/g
dry tannin gel under the conditions of 0.77 water content of tannin gel and the initial pH=2. This
adsorption capacity was five to ten times higher than that obtained by the ion exchange between ordinary
Cr(III) and tannin molecules for the tannin gels prepared under similar conditions. The system proposed
here will provide an important information on a zero-emission-oriented process because it has such
advantages as higher adsorption capacity of chromium and lower volume of secondary wastes compared
with conventional process. # 2000 Elsevier Science Ltd. All rights reserved

Key words}tannin, gel, hexavalent chromium, removal, redox, chromium, plant biomass

INTRODUCTION mium, neutralization of acidic solution and precipi-

Higher than allowable concentration of chromium
have been detected in ground soil and ground water.
Chromium usually exists in both trivalent and
hexavalent forms in aqueous systems. The hexavalent
form of chromium is of particular concern because of
its great toxicity. It is known to be carcinogenic and
mutagenic to living organisms.
The water treatments containing chromium which
is used in a variety of industrial applications, such as
electroplating, textile dying and metal finishing
industries, have been widely investigated from the
standpoint of environmental conservation. The con-
ventional process used to remove hexavalent chro-
mium is either its precipitation as chromium
hydroxide (Argo and Culp, 1972) or ion exchange
(Costa et al., 1998). These processes are not
completely satisfactory and have several disadvan-
tages; generation of large amount of secondary waste
products due to various reagents used in a series of
treatments such as reduction of hexavalent chro-
tation, and instability of ion exchange membrane due
to powerful oxidation of hexavalent chromium.
Thus, there is a need for the development of low
cost, easily available materials that can remove and
recover hexavalent chromium economically.
We have proposed a new recovery system of
hexavalent chromium utilizing condensed-tannin gel
derived from a natural polymer. Tannins are usually
extracted from leaves or cortexes in a variety of plants.
The tannin compounds containing a poly-hydroxy-
phenyl group have a high affinity for heavy metal ions
such as Cadmium, Cobalt, Chromium and Uranium
(Sakaguchi and Nakajima, 1987; Yamaguchi et al.,
1992; Sharma and Forster, 1993; Nakano et al., 1997).
The objective of the present investigation is to
understand the mechanisms that govern hexavalent
chromium removal by the condensed-tannin gel and
develop a recovery process of hexavalent chromium
based on a zero-emission-oriented concept.
MATERIALS AND METHODS

*Author to whom all correspondence should be addressed. Preparation of tannin gel

Tel.: +81-45-924-5432; fax: +81-45-924-5441; e-mail: Mimosa tannin (condensed-type tannin) was used as a
nakano@chemenv.titech.ac.jp starting material. It was dissolved in 24.6 ml of alkaline

496
 Adsorption mechanism of hexavalent chromium 497

Table 1. Compositions and water contents of tannin gel particles

Sample Amount of tannin (monomer) Amount of formaldehye Water content in wet basis (%)
(37 wt% solution crosslinker) (ml)

A 16.8 2.4 66.1

B 14.0 2.4 71.9
C 11.2 2.4 75.4
D 8.4 2.4 77.0

solution which was prepared by adding 1.8 ml of 6.25 N

NaOH into distilled water and then immobilized by the
reaction with formaldehyde (cross-linking agent). After
polymerization at 353 K for 12 h, the tannin gel obtained
was ground to small particles of 125 to 250 mm in diameter
and then, the gel particles were immersed in distilled water
to wash away unreacted substances. Finally, they were
employed as the materials to remove hexavalent chromium
in acidic solutions. The water content of tannin gel particles
was controlled by varying the ratio of the amount of
Mimosa tannin (monomer) to formaldehyde (cross-linking
agent). The difference in structure of the tannin gel particles
was represented by the water content of the tannin gel
particles. Table 1 shows the compositions and water
contents (wet basis) of the tannin gel particles.

Experimental procedure of Cr(VI) removal

The experiments of adsorption of chromium on tannin
gel were carried out by introducing a mass of 2.5 g (wet
basis) of the tannin gel particles into 100 ml of acidic
solution containing hexavalent chromium, Cr(VI). The
acidic solution was fully mixed in the batch reactor using
a magnetic stirrer under a constant temperature (303 K).
After the tannin gel particles were introduced into the batch
reactor, a small amount of solution was taken out through
the millipore filter at a time interval. The sample solutions
were analyzed for hexavalent and total chromium. Hex-
avalent chromium, Cr(VI) was detected by Diphenyl
Carbazide Method (Nihon Kikaku Kyokai, 1994). 1,5-
diphenyl carbazide forms a pink complex in the presence of
Cr(VI) ions in acidic solutions. The concentration of Cr(VI)
was calculated from absorbance at 542 nm using UV
spectrophotometer (U-2000A, Hitachi Co. Ltd.). Total
chromium, Cr(VI) and Cr(III) was determined by Inductiv-
ity Coupled Plasma Spectrometer (ICPS, SPA 4000, Seiko
Electric Co. Ltd.). The difference in concentrations between
the total and hexavalent chromium Cr(VI) was taken as the
concentration of trivalent chromium, Cr(III). The pH in
solutions was also monitored continuously all through the
experiments.
The experiments of adsorption equilibrium of chromium
were conducted to determine adsorption capacity of Cr(VI)
under a given set of conditions. Tannin gel particles (0.2–2 g
in wet basis) were in contact with 40 ml of the acidic solution
containing hexavalent chromium. When the tannin gel
particles and the solution reached equilibrium, the particles
were separated from the solution by filtration and the
adsorption capacity of Cr(VI) per gram of dry tannin gel
particles was evaluated for each tannin gels consisting of
different water contents.
The elution of chromium adsorbed on the tannin gel
particles was further carried out under 1 M HCl solution or
distilled water to confirm the states of chromium inside the
tannin gel particles.
RESULTS AND DISCUSSION
A batch experiment was conducted to understand
the mechanisms of the removal of Cr(VI) by the
Fig. 1. Time-varation of concentration of toal Cr, Cr(VI)
and Cr(III).
tannin gel particles. A mass of 2.5 g (wet basis) of
tannin gel particles and 100 ml of acidic solution
containing 1022 ppm of Cr(VI) were brought into
contact in the batch reactor. The initial pH of acidic
solution was set at pH=1 to elute chromium from
the tannin gel particles and identify the form of
chromium at 303 K. As shown in Fig. 1, the
concentration of Cr(VI) started to decrease rapidly
and Cr(VI) almost disappeared in the acidic solution
after 20 min. Instead of Cr(VI), Cr(III) appeared in
the acidic solution. This reveals that the reduction of
Cr(VI) into Cr(III) could occur during adsorption of
Cr(VI) on network of the tannin gel particles. Figure
2 shows the IR spectra of the virgin tannin gel
particles and the tannin gel particles contacted with
the acidic Cr(VI) solution during 3, 10 and 30 min.
The characteristic broad peak existed in the vicinity
of 3350 cm ÿ 1 arising from water molecules hydro-
gen-bonded with –OH groups in the virgin tannin gel
particles. The broad peak disappeared with the elapse
of time and a new peak appeared near 2900 cm ÿ 1.
This peak was confirmed to be derived from
coordination of the water molecules around Cr(III)
elements. In addition, the pronounced peak appeared
due to –C=O group at 1720 cm ÿ 1. This shows that
carbonic acid and ketone groups were created by
powerful oxidation of hexavalent chromium that
took place parallel to the reduction of hexavalent
chromium into trivalent one within the tannin gel
particles.
The effect of pH on the removal of Cr(VI) was
investigated by varying initial pH to understand the
498 Yoshio Nakano et al.
Fig. 2. IR Spectra of virgin tannin gel and tannin gels
contacted with acidic solution containing Cr(VI) for 3, 10
and 30 min.
Fig. 3. Time-varation of concentration of Cr(VI) in acidic
solution after pH in the solution is adjusted.
reduction process of Cr(VI) into Cr(III) within the
tannin gel particles. Figure 3 demonstrates that the
conversion of Cr(VI) depends on the pH remarkably.
When the reaction between tannin gel particles and
the acidic Cr(VI) solution started under the initial
pH=4.1, the reaction proceeded to attain equili-
brium at pH 7.9. When subsequent addition of 0.1 M
HNO3 was carried out to adjust the pH to 2.0, the
reaction proceeded further until the pH reached 7.2.
Table 2 shows the alterations in pH accompanied
with the conversion of Cr(VI). From the above
results, it was found that the removal of Cr(VI)
followed by the reduction of Cr(VI) into Cr(III)
requires a large amount of proton in the acidic
solution.
Table 2. Alternations in pH during the removal of Cr(VI) under
different initial pH
Sample Gel particles Initial pH Final pH
solution (g/ml)
0.85 1.1
2.0 7.2
B 0.5/40 2.9 8.0
4.2 8.0
5.0 8.0
The tannin gel particles in equilibrium with the
acidic solution of Cr(VI) were transferred into 1 M
HCl solution or distilled water to elute chromium
from them. Table 3 shows elution properties of
chromium under 1 M HCl solution or distilled water.
About 70% of chromium was extracted with 1 M
HCl eluent and all of them was trivalent chromium
produced by reduction of hexavalent one, Cr(VI). On
the other hand, a very small amount of hexavalent
chromium that remained unreacted within the space
of tannin gel network was eluted with distilled water.
Figure 4 shows the IR spectra of the tannin gel
particles collected before and after extraction of
chromium by 1 M HCl. Before extraction, a peak
existed due to the coordination of the water
molecules around Cr(III) elements in the vicinity of
2900 cm ÿ 1. After extraction, a peak appeared near
3350 cm ÿ 1 instead of it and this peak was confirmed
to be derived from water molecules hydrogen-bonded
with –OH groups. These results show that the
reduced Cr(III) can be adsorbed on the sites of –
OH and/or –COOH within the gel particles by ion
exchange mechanism.
Figure 5 shows the relationship between adsorp-
tion capacity of chromium and initial pH in the
acidic solution for the tannin gel particles having
various water contents of 66–77% whose composi-
tions are tabulated in Table 1. The highest adsorption
capacity of 287 mg Cr/g dry tannin gel particles
existed at the initial pH=2, even if the water content
of tannin gel particles altered. When the reaction
between the tannin gel particles and the acidic Cr(VI)
solution started under the initial pH higher than
pH=2, the reduced Cr(III) could not be eluted from
the tannin gel particles. From results of Figs 1, 3 and
5, we can conclude that the adsorption capacity
lowered due to the elution of chromium at the initial
pH below 2 and due to an insufficiency of proton
supply at the initial pH above 2.
The adsorption capacities of Cr(III) formed
through the reduction of Cr(VI) are compared with
those of ordinary Cr(III), as shown in Table 4. The
adsorption capacity of reduced Cr(III) was five to ten
times higher than that of Cr(III) for the same water
contents. This is one of the strongest pieces of
evidence in supporting that the formation of carboxyl
groups etc. through the oxidation of tannin mole-
cules yields the new ion-exchange sites of the reduced
Cr(III) and acts effectively to increase the adsorption
 Adsorption mechanism of hexavalent chromium 499

Table 3. Elution properties of chromium under 1 M HCl solution and distilled water

Eluant Elution time (h) Concentration of chromium (mg/l)

Total Cr Cr(VI) Cr(III)

1 M HCl 8 255 0 255

30 380 0 380
8 6.6 5.9 0.7
Distilled water 30 8.1 8.1 2.2

Table 4. Adsorption capacity of Cr(VI) and Cr(III) for tannin gel

particles of different water content

Element Water content (%) Adsorption capacity

(mg Cr/g dry tannin)

Cr(VI) 66.1 192

71.9 224
75.4 235
77.0 287
Cr(III) 66.1 19.8
71.9 27.9
75.4 38.0
77.0 50.0

Fig. 4. IR spectra of the tannin gel particles befor

(adsorption state) and after (desorption state) extraction
of Cr(VI) by 1 M HCl.

Fig. 6. Mechanism of removal of Cr(VI) bu tannin gel

particle.

Fig. 5. Effect of initial pH on the adsorption capacity of

Cr(VI). The signs of (A)–(D) in the figure correspond to
those shown in Table 1.
capacity. The maximum adsorption capacity of
chromium was 287 mg Cr/g dry tannin gel particles
for the tannin gel particles having high water content
of 77%. This adsorption capacity was found to be
very high compared with adsorbents commonly used
such as an activated carbon (Huang and Wu, 1977)
and ion exchange resin (about 50 mg Cr/g dry resin).
Figure 6 is a schematic diagram showing the
removal of Cr(VI) within the tannin gel particles
which can be presumed from the above results. The
removal mechanism consists of four steps, the
esterification of chromate with tannin molecules,
the reduction of Cr(VI) into Cr(III), the formation of
carboxyl group by the oxidation of tannin molecules
500 Yoshio Nakano et al.
and the ion exchange of Cr(III) with hydroxyl and/or
carboxyl groups created in tannin gel particles. In
this reaction process, it is very important to supply a
large amount of proton for promoting the reduction
of Cr(VI) into Cr(III). This shows that the pH in the
acidic solution can be increased to produce neutral
solution through the adjustments of the amount of
tannin gel particles and the volume of acidic solution
having an appropriate pH for the concentration of
Cr(VI). From the above results, we can design a
recovery system of Cr(VI) which consists of four
units; adjustment of pH (pH=2) in the waste liquid
containing Cr(VI), reaction between the tannin gel
particles and the acidic solution, separation of the
tannin gel particles adsorbing the reduced Cr(III) and
disposal of the tannin used as well as recovery of
Cr(III) from the tannin gel particles through their
decomposition by combustion or biodegradation.
The waste reduction capabilities of this system
were compared with a conventional chromium
removal system consisting of the reduction of Cr(VI)
to Cr(III), the neutralization of acidic solution and
precipitation. In the system proposed herein, a small
amount of H2SO4 is used to adjust the waste water
pH to 2. The tannin gel particles containing the
reduced Cr(III) are decomposed to recover the
chromium by their decomposition. It is necessary to
increase the adsorption capacity of Cr(VI) much
more in order to reduce the amount of tannin gel
particles used.
For a conventional system, a large amount of
secondary waste products are generated in the forms
such as Cr(OH)3 (sludge) and Na2SO4
CaSO4
because reducing and neutralizing agents are com-
monly used.
CONCLUSION
The mechanism that governs hexavalent chromium
Cr(VI) removal by the condensed-tannin gel was
clarified. It consists of four steps: the esterification of
chromate with the tannin molecules in the presence of
proton, the reduction of Cr(VI) into trivalent
chromium Cr(III), the formation of carboxyl group
by the oxidation of tannin molecules and the ion
exchange of reduced Cr(III) with hydroxyl and/or
carboxyl groups created in the condensed tannin gel
particles. The adsorption capacity of chromium was
affected strongly by the concentration of proton (pH)
in the acidic solution containing the hexavalent
chromium Cr(VI). The adsorption capacity lowered
remarkably due to the elution of the reduced Cr(III)
below pH=2 and due to an insufficiency of proton
supply above pH=2. The maximum adsorption
capacity, 287 mg Cr/g dry tannin gel, existed at the
initial pH=2. Increase of the adsorption capacity of
hexavalent chromium resulted in the formation of
carboxyl groups by the oxidation of tannin molecules
which yielded a large amount of ion-exchange sites of
the reduced Cr(III). It was shown that the acidic
solution was able to be improved into neutral one,
and hexavalent chromium in the acidic solution was
reduced completely into trivalent one and fixed inside
the tannin gel by adjusting the amount of tannin gel,
the volume of acidic solution containing Cr(VI) and
initial pH in the solution. This recovery system of
Cr(VI) would be very useful to develop a zero-
emission-oriented process.
REFERENCES
Argo D. G. and Culp C. L. (1972) Heavy metal removal.
Wastewater Treatment Processes Water and Sewage
Works 119, 62–65.
Costa R. D., Rodrigues M. A. S. and Ferreria J. Z. (1998)
Transport of trivalent and hexavalent chromium through
different ion-selective membranes in acidic aqueous
media. Sep. Sci. Technol. 33, 1135–1143.
Yamaguchi H., Higasida R., Higuchi M. and Sakata I.
(1992) Adsorption mechanism of heavy-metal ion by
microspherical tannin resin. J. Appl. Polymer Sci. 45,
1463–1472.
Sharma D. C. and Forster C. F. (1993) Removal of
hexavalent chromium using sphagnum moss peat. Water
Res. 27, 1201–1208.
Nakano Y., Takeshita K., Tsutsumi T. and Nakamura Y.
(1997) Adsorption of Cr(VI) by condensed-tannin gel.
Proceedings of the 30th Autumn Meeting of Chemical
Engineers, The Society of Chemical Engineers, Japan
Q-217, 229.
Sakaguchi T. and Nakajima A. (1987) Recovery of uranium
from seawater by immobilized tannin. Sep. Sci. Tech. 22,
1609–1623.
Nihon Kikaku Kyokai (1994) JIS Handbook 10. pp.
1066–1069, Tokyo, Japan.
Huang C. P. and Wu M. H. (1977) The removal of
chromium from dilute aqueous solutions by activated
carbon. Water Res. 11, 673–679.