ENVIRONMENTAL ENGINEERING SCIENCE

Volume 24, Number 10, 2007

© Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2006.0280

Natural Mordenite Derived Zeolites: Synthesis,

Formation, and Their Evaluation in Cr(III)
Removal from Tannery Wastewater

Cristian Covarrubias,1,* Renán Arriagada,1 Jorge Yánez,1 María Teresa Garland,2

and Rafael García1

1Facultad
de Ciencias Químicas
Universidad de Concepción
Concepción, Chile.
2Departamento de Física

Facultad de Ciencias Físicas y Matemáticas and CIMAT

Universidad de Chile
Santiago, Chile

ABSTRACT

The synthesis of zeolites from natural mordenite, their subsequent forming process, and their evalua-
tion in a Cr(III) removal process from tannery wastewater is presented. Mordenite is an abundant nat-
urally occurring zeolite with relatively low cation exchange properties. Zeolite synthesis from mor-
denite was carried out in a larger reactor than commonly employed autoclaves. Synthesized products
were identified by X-ray diffraction (XRD), and zeolite extrudates were characterized by their chromium
exchange capacity (CrEC), mechanical, and textural properties, which were optimized as a function of
binder composition. A FAU zeolite-rich product was obtained under controlled synthesis conditions.
FAU-type zeolite is a nanoporous material (pore opening of 0.74 nm), which presents high cation ex-
change capacity. The use of silicate–urea-based binders enabled the production of FAU-type zeolite ex-
trudates with CrEC (0.64 mEq  g1) and compressive strength (143 kg  m2) appropriate for their use
in Cr(III) removal processes from aqueous solution; these values were as high as those found for com-
mercial zeolite extrudates (0.65 mEq  g1 and 66 kg  m2, respectively). Columns packed with the
prepared zeolite extrudates, exhibited high performance for Cr(III) removal from synthetic and diluted
tannery wastewater (pH 3.5). Thus, FAU-type zeolite extrudates obtained from natural mordenite ap-
pear as promising ion exchangers for tannery wastewater treatment and as a feasible alternative to the
commercial ion exchangers.

*Corresponding author: Center for Advanced Interdisciplinary Research in Materials (CIMAT), University of Chile, Av. Blanco
Encalada 2008, piso zócalo, Santiago, Chile; Phone: 56 41 978 4795; Fax: 56 02 699 3982; E-mail address: crcovarr@cimat.cl

1443
1444
Key words: removal of chromium (III); zeolite syn-
thesis; zeolite extrudates; wastewater treatment
INTRODUCTION
C HROMIUM IS ONE OF THE MOST STUDIED heavy metals
because of its relative frequency and high toxicity
(Seiler et al., 1988; U.S. EPA, 1998). It is present com-
monly as Cr(VI) and Cr(III). Hexavalent chromium is
well known by its high toxicity as well as by its muta-
genic and carcinogenic properties (ATSD, 2000). Al-
though hexavalent chromium is the most hazardous
chromium species, the trivalent chromium also requires
particular attention: Cr(III) and Cr(VI) are easily inter-
convertible. Alkaline medium, aerobic conditions, and
higher temperatures favor the oxidation of Cr(III) to
Cr(VI) (Nieboer and Shaw, 1988; Katz and Salem, 1994;
Lee and Jones-Lee, 1997). The conversion of Cr(III) to
Cr(VI) in chromium-contaminated sludge has also been
demonstrated (Avudainayagam et al., 2003; Apte et al.,
2006; Lai and Mcneill, 2006). In this case, Cr(III) oxi-
dation is feasible in the presence of MnO2 and under aer-
obic conditions. There is a real danger under field con-
ditions of spreading Cr(VI) pollution due to possible
intervening rainfall, runoff, and percolation.
Currently, chromium tanning is the most widely used
technique for leather tanning, as it offers a product with
the best performance at a reasonable price. However, a
significant share of the pollution resulting from tannery
wastewater comes from this stage, due to the chromium
that is not fixed to leather (15%) (Roig et al., 2001).
Tannery wastewater is usually homogenized with the
rest of industrial effluents and Cr(III) precipitates as
chromium hydroxide, thus being retained in the sludge
of the water treatment plants (REPAMAR, 1995).
Although precipitation treatment is quite satisfactory
in terms of purging Cr(III) and other metals from water,
solid residues (sludge) are produced which contain
chromium compounds, whose final disposal is generally
by landfilling. This procedure has high costs, and is still
a possibility of groundwater contamination. This im-
pressive environmental requires that tanneries improve
the available technology, to reduce the environmental im-
pact and disposal costs. Additionally, the use of precipi-
tation methods does not reduce the chromium levels
enough to meet the strict limits demanded by the actual
legislation (0.5–2.5 mg  dm3 for total Cr and 0.1 mg 
dm3 for Cr(VI) in liquid industrial emissions) [Envi-
ronmental National Commission (CONAMA, 2003)].
This is an area where ion exchange processes can be em-
ployed successfully, due to the fact that their application
is simple, suits automation and quality control, and op-
COVARRUBIAS ET AL.
erates under relatively mild conditions (Leinonen, 1999;
Bolto and Pawlowski, 1987). Zeolitic materials are the
most important inorganic cation exchangers that exhibit
high ion exchange capacity, selectivity toward different
metallic ions, and compatibility with the natural envi-
ronment (Newsam, 1992). Cr(III) removal using differ-
ent commercial zeolites (synthetic and naturally occur-
ring) has been studied in previous works (García et al.,
1999; Barros et al., 2004; Covarrubias et al., 2005). It
was found that the synthetic faujasite-type zeolite (FAU
zeolite) presents the highest chromium exchange capac-
ity (CrEC). The chromium exchange on FAU-type zeo-
lites is favored due to the significantly large pore open-
ing of 0.74 nm, which facilitates the retention of sizably
hydrated Cr(III) ions from solution. The Cr (III) ion has
been reported to possess the largest number of tightly
bound water molecules (or the apparent dynamic hydra-
tion number, ADHN  9.59  0.31) (Kiriukhin and
Collins, 2002) and the largest hydrated ionic radius
(0.461 nm) among the known heavy metals (Nightingale,
1959), and its exchange in zeolitic materials require a fa-
vorable pore opening.
Zeolitic materials can be synthesized from pure reagents
using silicon sources (silicate solutions, tetraethylorthosil-
icate, fumed silica, precipitated silica, and colloidal silica
sol) (Kuhl et al., 200; Krznarć et al., 2003), aluminum
sources [aluminate solutions, alumina oxides, Al3 salts,
and Al(EtO)3] (Reddy and Song, 1996; Lu et al., 2004)
and mineralizer agents such as NaOH, KOH, TMAOH,
TPAOH, or HF (Byrappa et al., 2004). Zeolite synthesis
can also be carried out using natural aluminosilicates as a
source of silicon and aluminum species. Some of these raw
natural materials include kaolin (De Lucas et al., 1992;
Rees and Chandrasekhar, 1993a, 1993b; Sanhueza et al.,
1999; Lin et al., 2004), diatomite (Sanhueza et al., 2003),
halloysite (Novembre et al, 2005), as well as coal fly ash
(Amrhein et al., 1992). Another way to synthesize zeolites
is the transformation of one zeolite type into another zeo-
lite type (Subotić et al., 1982). In a previous work (Co-
varrubias et al., 2006) it was found that different zeolites
can be synthesized from kaolin and also by the transfor-
mation of natural mordenite. Mordenite is a member of the
aluminosilicate zeolite class of minerals with structural for-
mula usually give as (Na2,Ca,K2)Al2Si10O24.7H2O (Breck,
1974), and possesses relatively low cation exchange prop-
erties. Zeolites FAU (NaY), P, and hydroxysodalite were
obtained under controlled hydrothermal treatment of low-
cost natural mordenite. The synthesized zeolite powders
presented high Cr(III) exchange capacity (CrEC) (3.0–4.1
mEq  g1) to be evaluated in water purification applica-
tions.
Scale-up attempts of some known zeolite synthesis
conditions, as well as forming experiments with the very
ZEOLITES FOR CHROMIUM REMOVAL FROM WASTEWATERS
fine and powdery zeolite materials are aspects less ad-
dressed in literature. In a recent report (Casci, 2005) gen-
eral aspects of zeolite molecular sieves preparation and
scale up are described from an industrial perspective. This
paper states that forming processes such as the prepara-
tion of extrudates are of crucial importance for the use
of synthesized zeolite powders in adsorption/ion ex-
change applications. Extrudates of zeolite X have been
prepared by means of the transformation of metakaolin
extrudates (Akolekar et al., 1997). In the preparation of
the kaolin extrudates, a reported procedure was used (Coe
et al., 1988). Kaolin, starch maize, and water were ap-
propriately mixed to form 1–5 mm-diameter kaolin ex-
trudates, which were thermically converted into
metakaolin pellets. The subsequent hydrothermal treat-
ment of the preshaped metakaolin extrudates produced
well crystallized zeolite pellets, retaining the original
morphology of the extrudates; although no references
with respect to mechanical properties of these hy-
drothermally obtained extrudates are given. In another
work (Basaldella et al., 1995) the precedent procedure
was used (Coe et al., 1988), and crystallization of 60%
of low-silica zeolite X over metakaolinite pellets was ob-
tained. It was also proved that seed utilization enhances
the zeolite formation on the pellets but produces simul-
taneously powdered zeolite in the solution.
In the present work, a scaling-up attempt of the zeo-
lite synthesis from natural mordenite is presented, as well
as the preparation of zeolite extrudates and its evaluation
in a Cr(III) removal process. Zeolite synthesis was car-
ried out in a reactor somewhat larger than commonly em-
ployed autoclaves, and the obtained products are com-
pared with those of the traditional autoclaves. Zeolite
extrudates were obtained using a silicate–urea-based
binder and columns packed with the zeolite extrudates
were evaluated in a dynamic Cr(III) removal process
from synthetic and diluted tannery wastewaters.
EXPERIMENTAL PROTOCOLS
Synthesis of zeolites
The synthesis of zeolite was carried out using natural
mordenite as starting material. Table 1 shows the chem-
Table 1. Chemical composition of natural mordenite (%wt).
SiO2 Al2O3 TiO2 MgO
Natural 70.6 12.7 0.3 0.7
Mordenite
1445
ical composition of the natural zeolite obtained by X-ray
fluorescence. Mordenite zeolite was obtained from nat-
ural deposit situated about 300 km south of Santiago,
Chile. To obtain a more reactive phase, natural morden-
ite (crushed and sieved to 0.038 mm of particle diame-
ter), was used after calcination at 900°C for 30 min. The
reaction mixture was prepared by adding 43.6 g of cal-
cined mordenite to 900 cm3 of alkaline aluminate solu-
tion, which was prepared by dissolving 9.7 g of aluminum
bands (Merck, Rahway, NJ) in alkaline solutions con-
taining 0.5 to 2.0 mol  dm3 NaOH. The resulting mix-
ture was placed in a Teflon-lined stainless steel reactor
and kept in an oven for static hydrothermal synthesis at
100°C for 15 h, using the optimal conditions reported in
a previous study (Covarrubias et al., 2006). In the pres-
ent work, the used Teflon-lined stainless steel reactor
(1,000 cm3) was larger than the commonly employed lab-
oratory autoclaves (45–125 cm3). The effect of alkalin-
ity of the reaction mixture (Na2O/Al2O3 molar ratio) on
the synthesis products was also investigated. For the re-
action mixture with molar composition: xNa2O:Al2O3:
2.5SiO2:243.7H2O, where x  Na2O/Al2O3, values of x
in the range of 1.15–4.44 were used.
After completion of the synthesis period, the product
was filtered, washed, and dried overnight at 100°C. The
zeolitic phases in synthesis products were identified by
using X-ray diffraction (XRD). Powder X-ray diffraction
were measured on a Siemens D 5000 diffractometer us-
ing Cu K radiation within a 2 range of 5–50 with a
scanning speed of 1.2°/min.
Preparation of zeolite extrudates
To obtain zeolite extrudates, two types of binder solu-
tions were used: (1) dilutions of sodium silicate solution
(sodium silicate 28 wt%, Merck) (binder SiH), and (2)
urea-silicate binder (binder SiUr), which was prepared by
dissolving different amounts of urea (NH2CONH2,
Scharlau) in sodium silicate solution under constant stir-
ring. The zeolite powders were thoroughly mixed with
binder solutions to obtain a paste with adequate reologi-
cal properties to allow its extrusion. Zeolite extrudates
were obtained by using a press-type extrusion process
(Perry, 1963). For this purpose, the resulting homoge-
nous mixture paste was placed into a stainless steel mold,
Molar
CaO Fe2O3 Na2O K 2O MnO SiO2/Al2O3
3.3 1.2 1.5 1.1 0.2 9.4
ENVIRON ENG SCI, VOL. 24, NO. 10, 2007
1446
where it was forced to pass through a die with aid of a
piston, which was manually operated by using a hydraulic
press (Carver Laboratory Press, Model M). Continuous
and cylindrical extrudates of 1.6-mm diameter were ob-
tained at the exit of the die, which then were cut to length.
The prepared extrudates were dried in air at room tem-
perature and subsequently activated by ion exchange and
thermal treatment. Ion exchange was carried out in a
NaCl solution of concentration 1.0 mol  dm3 at 25°C
for 24 h. Afterward, the extrudates were washed with
deionized water and dried at 110°C for 1 h, and subse-
quently submitted to thermal treatment at 400°C for 4 h,
with a heating rate of 10°C  min1.
Properties of zeolite extrudates and optimization
of binder composition
The optimization of the binder composition (Table 2)
was carried out on the chromium exchange capacity
(CrEC), compressive strength (Ps), and specific surface area
(Sg) of the extrudates by using commercial FAU zeolite
powder (Molecular Sieve 13X, BDH Dagenham, Essex,
UK). These properties were also determined for extrudates
of zeolite synthesized from mordenite, which were prepared
using the optimum binder composition (binder SiUr20-12).
CrEC of the extrudates and zeolite powders was de-
termined from ion exchange experiments. For this pur-
pose, 0.5 g of zeolite (extrudate or powder) were con-
tacted with 80 cm3 of 500 mgdm3 Cr(III) solution,
which was prepared from the basic salt chromium sulfate
Cr(OH)SO4Na2SO4, a salt commonly used in the indus-
trial tanning process. According to previous study on the
exchange rate of Cr(III) in zeolites (García et al., 1999),
chromium exchange was carried out for 24 h at 25°C in
a thermostatically controlled shaker water bath. Com-
pressive strength of the extrudates was measured by us-
ing a Monsanto instrument, whose values correspond to
Table 2. Binder compositions used in preparation of zeolite
extrudates.
Concentration of sodium silicate
solution (SiO2 wt%)
SiH-28 28
SiUr28-6 28
SiUr28-7 28
SiUr28-10 28
SiUr28-15 28
SiH-20 20
SiUr20-11 20
SiUr20-12 20
SiUr20-16 20
Binder volume/zeolite mass ratio: 0.73 cm3  g1.
COVARRUBIAS ET AL.
the applied mass per extrudate area to produce the break
of the cylindrical extrudate (kg  cm2). Textural char-
acterization of synthesized zeolite powders and extru-
dates was carried out by N2 adsorption at 77 K in a Mi-
cromeritics Gemini 2370 sorptometer. The Sg values were
calculated applying the BET equation to the experimen-
tal data obtained from N2 isotherms. Thermogravimetric
curves (TG) of the zeolite extrudates were obtained us-
ing a Mettler Toledo TG/SDTA851 thermogravimetric
analyzer, and a heating rate of 10°C  min1.
Chromium removal through zeolite-packed bed
Dynamic sorption of chromium ions was studied in
columns packed with extrudates of zeolite synthesized
from natural mordenite. For purposes of comparison,
chromium retention was also evaluated in a column
packed with pellets of the commercial zeolite 13X
(BDH). In order to obtain an optimum particle size ac-
cording with lab-scale columns, the pellets were crushed
and sieved to an average particle size in the range 0.2–0.5
mm. According to previous study (Covarrubias et al.,
2005), the use of smaller particle size affords a reduction
in the mass transfer resistances during Cr(III) exchange
process in the zeolite column. The column dimensions
were of 1 cm i.d. and 12 cm long, with a total zeolite bed
height of 8 cm and with a packing density of 0.75 g 
cm3. A hybrid system composed of activated carbon
and zeolite columns in series connected was also evalu-
ated. In this case a commercial activated carbon of peach
stone (Cudu754, Petrochil SA, Rengo, Chile) was used.
Dynamic retention of Cr(III) was carried out by pump-
ing chromium solution up through the column (300 cm3 
h1), using a peristaltic pump (Masterflex, Cole-Parmer,
Vernon Hills, IL, 7521-10). In order to obtain the break-
through curves, samples of 20 cm3 were taken from the
column outlet at 4-min intervals by using an automatic
Urea (wt%)
0.0
6.0
7.5
10.5
15.0
0.0
11.3
12.9
16.2
ZEOLITES FOR CHROMIUM REMOVAL FROM WASTEWATERS
fraction collector (Spectra/Chrom CF-1) and the
chromium concentration in these samples was measured
using a Perkin-Elmer (Norwalk, CT) Analyst 100 atomic
absorption spectrophotometer (AAS). The Cr(III) re-
moval was evaluated on a synthetic Cr(III) solution of
concentration 30 mg  dm3 and on a tannery wastewater
diluted to 100 mg  dm3 of Cr(III), whose chemical
characterization is shown in Table 3. Chemical demand
of oxygen (COD) of selected samples was determined us-
ing the standard method (APHA, 1992). The pH of both
feed solutions was adjusted to 3.5.
RESULTS AND DISCUSSION
Zeolite synthesis
Table 4 compares the mass, CrEC, Sg, and relative
crystallinity of synthesized products obtained in the ini-
tial 100 cm3 autoclave (R100) with the products obtained
in the reactor of 1,000 cm3 (R1000) at different Na2O/
Al2O3 ratios (NaOH concentrations). The properties of
the commercial zeolite 13X are also shown as reference.
Relative crystallinity values to the zeolite 13X of refer-
ence were calculated using the intensities values of the
more characteristic and intense (111) FAU-peak at 6.12°.
As can be observed, the zeolite synthesis initially carried
out in the R100 reactor gave a product amount of around
3 g. This product mass is almost proportionally increased
by using the R1000 reactor, in which product amounts of
around 30 g were obtained. It is important to note that
the maximum chromium exchange capacity, surface area,
and crystallinity values for the R1000 products were ob-
tained when 1.0 mol  dm3 NaOH concentration was
used, while the best conditions for the R100 reactor cor-
responded to 2.0 mol  dm3 NaOH concentration (Co-
varrubias et al., 2006).
The XRD analysis of the synthesized products (Fig. 1)
reveals that FAU-type zeolite is the predominant phase in
the products obtained with NaOH concentrations of 2.0
mol  dm3 and 1.0 mol  dm3 in the R100 and R1000
reactors, respectively. The fraction of FAU-type zeolite and
its crystallinity degree (Table 4) in these synthesized prod-
ucts, explains the higher specific surface area and chromium
exchange capacity of these solids. The Zeolite FAU struc-
ture has large pore apertures (0.74 nm), which favor the
Table 3. Chemical characterization of diluted tannery wastewater.
Cr Ca Mg
(mg  dm3) (mg  dm3) (mg  dm3) (mg  dm3)
100.6 63.3 13.7
1447
diffusion of hydrated Cr(III) into the internal zeolite ex-
change sites. When NaOH concentrations were higher than
1.5 mol  dm3, the formation of zeolite P phase was ob-
served in the products. Zeolite P has lower specific surface
area and Cr(III) exchange capacity than FAU-type zeolite
(Covarrubias et al., 2006), which explains the overall de-
crease in Sg and CrEC values of the synthesized products.
The differences between the optimal synthesis conditions
obtained in each reactor confirm the effect of the geome-
try and dimensions of the reactor (Gianneto et al., 2000)
on the course of the zeolite crystallization/transformation
process. The reactor dimensions can affect the distribution
of silicon and aluminum species into the reactor, as well as
its transferring to growing crystals. Different temperature
fluctuations across the reactor can also be produced, and
consequently, the crystallization of different zeolite phases
under similar experimental conditions. Differences in the
synthesis results obtained in R100 and R1000 reactors can
be attributed to the effect of the heterogeneity of synthesis
medium (composition and heat distribution) produced by
the uneven settling of the synthesis medium during the sta-
tic hydrothermal period, which is more significant when
the larger R1000 autoclave is being used. Thus, uneven set-
tling of the solid and/or gel phases causes heterogeneity in
the composition affecting the course of the crystallization
process. These results suggest the importance to carry out
scale-up attempts of well-known synthesis conditions, as
well as further studies about mixing effects (Bebon et al.,
2002) on the hydrothermal crystallization process. On the
other hand, it is worthwhile to mention that the concentra-
tion of NaOH in the solution decreased by less than 1% af-
ter being used in three successive syntheses. This indicates
that NaOH solution could be recovered and reused for sev-
eral synthesis runs.
Preparation of zeolite extrudates
In order to use a more homogenous zeolite power in
the study of binder composition for the preparation of
zeolite extrudates, binder optimization was carried out
using commercial 13X zeolite powder. The typical
binder/zeolite ratio, which yielded the best extrusion con-
ditions, was of 0.73 cm3 binder/g zeolite.
In Fig. 2, the results of the optimization of the com-
position of the silicate (SiH) and urea–silicate (SiUr)-
based binders as a function of CrEC, specific surface area
K Na COD
(mg  dm3) pH (mg  dm3)
7.1 937.5 3.50 1805
ENVIRON ENG SCI, VOL. 24, NO. 10, 2007
1448 COVARRUBIAS ET AL.

Figure 1. XRD diffractograms of (a) starting mordenite; synthesis products obtained in (b) R100 reactor with 2.0
mol  dm3 NaOH concentration, in R1000 reactor with NaOH concentration of (c) 2.0 mol  dm3, (d) 1.7 mol  dm3, (e) 1.5
mol  dm3, (f) 1.0 mol  dm3, (g) 0.7 mol  dm3, (h) 0.5 mol  dm3 (t: 15 h, T: 100°C); (i) standard 13X zeolite.

(Sg) and compressive strength (Ps) of the zeolite extru-
dates are shown. To better clarity in the figure, CrEC val-
ues are expressed in microequivalents per gram. It can
be observed that the presence of urea in the silicate based
binder increases both the CrEC and specific surface area
of the extrudates. The effect of the urea content on the
surface area of the extrudates can be attributed to an in-
crease in the extrudate microporosity (interparticle
spaces) after urea decomposition. Differential thermo-
gravimetric (DTG) curves obtained for the extrudates are
shown in Fig. 3. It can be observed that extrudates pres-
ent weight losses within the 100–210°C temperature
range, which correspond to zeolite dehydration steps
(Breck, 1974). In addition, SiUr20-12 extrudate exhib-
ited a DTG peak around 350°C, which is characteristic
of the urea decomposition. This urea decomposition event
was caused by micropores formation in the interior of the
extrudates, which favors the contact between zeolite par-
ticles and fluid during adsorption and ion exchange pro-
cesses (García-Martinez et al., 2002). Due to the fact that
the quantity of FAU zeolite is (assumingly) the same in
all extrudates, lower CrEC obtained for zeolite extrudates

Table 4. Mass, Cr(III) exchange capacity (CrEC), specific surface area (Sg) and FAU-crystallinity of synthesis products
obtained in reactors with different dimensions.

Reactor volume

100 cm3 1,000 cm3 Z13X powder

Average product mass (g) 3

NaOH concentration (mol  dm3) 2.0 0.5 0.7 1.0 1.5 1.7 2.0
CrEC (mEq  g1) 3.88 3.01 3.65 3.83 3.75 3.45 3.23 3.52
Sg (m2  g1) 316 12 166 270 141 132 32 578
Relative FAU phase crystallinity (%) 84 19 44 55 47 20 24 100
ZEOLITES FOR CHROMIUM REMOVAL FROM WASTEWATERS
Figure 2. Optimization of binder composition as a function of Cr(III) exchange capacity (CrEC), specific surface area (Sg) and
compressive strength (Ps) of zeolite extrudates by using standard 13X zeolite powder.
having lower microporosity can be attributed to that max-
imum exchange was not achieved after 24 h of ion ex-
change process (Cussler, 1984). Further studies about ki-
netic of the ion exchange process (García et al., 1999)
could be performed in order to investigate the optimum
conditions (contact time and ion exchange temperature)
for maximum Cr(III) exchange in the zeolite extrudates.
On the other hand, compressive strength (Ps) of zeo-
lite extrudates was higher, when silicate solution of con-
centration 28% was used (SiUr28). Binders prepared with
more diluted silicate solution (20%) and with higher urea
Figure 3. Thermogravimetric analysis of zeolite extrudates
(DTG).
1449
content (SiUr20) resulted in higher chromium exchange
capacity, and in some cases in higher Sg values of the ex-
trudates, maintaining an adequate compressive strength.
In order to get an agreement between CrEC, Ps, and Sg
extrudate properties, the binder SiUr20-12 was chosen to
prepare extrudates with the synthesized zeolite powders
from natural mordenite (Pellet Syn-Mor). The FAU ze-
olitic product derived from mordenite was obtained in
R1000 reactor by using NaOH concentration of 1.0 mol 
dm3. In Fig. 4 the CrEC, Sg, and Ps properties of zeo-
lite extrudates synthesized from mordenite (Syn-Mor) are
compared with those of standard 13X zeolite. It can be
observed that CrEC values of the original 13X zeolite
powder (3.52 mEq  g1) is reduced in about 5.4 times
by formed process effect (0.65 mEq  g1), during the
commercial extrudate preparation. Whereas CrEC of the
13X extrudates (0.29 mEq  g1) was about 12.1 times
lower than that of powdered 13X zeolite when the
SiUr20-12 binder is being used. However, when zeolite
extrudates were prepared from synthesized zeolite pow-
der (Syn-Mor, 3.83  mEq  g1), CrEC of the obtained
extrudates (0.64 mEq  g1) was about 6.0 times lower
in relation to the starting zeolite powder and very close
to that of the commercial extrudate. The higher CrEC of
the Syn-Mor extrudates is consequence of significantly
higher CrEC of the starting Syn-Mor powder compared
with that of the powdered 13X zeolite.
On the other hand, specific surface area of extrudate
Syn-Mor was lower than that of extrudate prepared by
using 13X zeolite powder and than that of the commer-
cial extrudate of reference. This difference can be attrib-
ENVIRON ENG SCI, VOL. 24, NO. 10, 2007
1450 COVARRUBIAS ET AL.

Figure 4. Comparison of CrEC, Sg, and Ps properties of zeolite extrudates synthesized from mordenite (Syn-Mor) with those
of standard 13X zeolite.

uted to the lower surface area of the zeolite synthesized
from mordenite (Sg  270 m2  g1), compared with the
surface area of 13X zeolite powder (Sg  578 m2  g1).
Moreover, the fact that in the case of the commercial ex-
trudate a different binder is being used must be also con-
sidered. However, as has been previously found (Covar-
rubias et al., 2006) specific surface area of the zeolites
has minor effect on the actual chromium exchange ca-
pacity of these materials. On the other hand, the prepared
Syn-Mor extrudates exhibited a compressive strength
(Ps) about factor 2.14 higher than Ps value of commer-
cial extrudate. Moreover, Syn-Mor extrudate showed an
outstanding stability in aqueous media as revealed by vi-
sual inspection of them after 24 h of ion exchange in
batch conditions as well as after prolonged retention pro-
cesses under dynamic column conditions. These proper-
ties make these materials appropriate to be used in a
packed-bed reactor and during a chromium removal pro-
cess from aqueous solution.
Chromium removal through zeolite packed-beds
Columns were packed with the prepared Syn-Mor ex-
trudates (SiUr20-12) and with the commercial 13X ex-

Figure 5. Cr(III) breakthrough curves on packed-beds loaded with zeolite extrudates ([Cr]f :30 mg  dm3, f: 300 cm3  h1).
ZEOLITES FOR CHROMIUM REMOVAL FROM WASTEWATERS 1451

Table 5. Mass transference parameters for Cr(III) removal from synthetic chromium
solution through zeolite-packed beds.

Cr3
dp Kca tb Vb retention
Zeolite column (mm) %HUNB (min1) (h) (dm3) (mg)

Z13X 0.5 39 4.1 20.1 6.03 181

Syn-Mor 0.5 41 3.9 22.5 6.75 202
Z13X 0.2 18 8.6 33.4 10.2 301
Syn-Mor 0.2 24 6.4 36.5 10.95 328

Cr concentration in the feed solution: 30 mg  dm3 ([Cr]f); flow of feed solution: 300 cm3 
h1(f); dp: particle diameter; tb: breakthrough time; Vb: volume of solution treated up to tb.

trudates of reference and evaluated in Cr(III) removal
from aqueous solution. The Cr(III) concentration in the
synthetic feed solution was of 30 mg  dm3, which is a
typical concentration found in tannery wastewaters after
precipitation treatment (Covarrubias et al., 2005). Fig. 5
shows Cr(III) breakthrough curves obtained on the
packed columns operating with two different particle
sizes. It can be observed that Syn-Mor columns present
higher Cr(III) removal efficiency than that exhibited by
the Z13X column of reference. Due to the fact that the
CrEC of Syn-Mor and Z13X extrudates is similar (0.64
and 0.65 mEq  g1, respectively), higher Cr(III) removal
efficiency presented by the Syn-Mor extrudates under dy-
namic conditions could be attributed to the phenomenon
of surface precipitation, which commonly occurs during
column operation. Recent experimental evidence has in-
dicated that surface nucleation of metal hydroxides oc-
curs much more frequently than previously believed
(Fendorf et al., 1994). The formation of small multinu-
clear cationic species by polymerization on solid surface,
such as dimers or trimers, may lead to the formation of
metal hydroxide. We have also observed that Cr(III) pre-
cipitation on zeolite bed is a phenomenon that commonly
occurs during column operation (Covarrubias, 2005).
Thus, higher concentration of surface hydroxyl groups in
Mor-derived zeolite products obtained after prolonged
and alkaline hydrothermal treatment (Covarrubias et al.,
2006) would favor in higher degree the surface precipi-
tation mechanism increasing the observed chromium re-
moval during Syn-Mor column operation. On the other
hand, from the shape of 13X breakthrough curves can be
also observed that smaller particle diameters give break-
through curves with steeper slopes, indicating that mass
transfer conditions through the zeolite bed are improved.
This is because the ion exchanged specie takes shorter
time to diffuse into the zeolite and become exchanged on
all available active sites. Particle size effect on mass
transfer process is minor for Syn-Mor columns and
broader breakthrough curves are obtained, which can be
the consequence of the precipitation phenomenon pro-
duced during the operation. In Table 5 the effect of zeo-
lite particle diameter on mass transfer parameters and
chromium removal performance of the columns is pre-
sented. The fraction of unused bed (%HUNB) (McCabe et

Figure 6. Cr(III) removal from tannery wastewater through zeolite-packed beds and using a hybrid system of activated carbon
and zeolite columns in series connected ([Cr] f : 100 mg  dm3, f : 300 cm3  h1, dp: 0.2 mm).

ENVIRON ENG SCI, VOL. 24, NO. 10, 2007

1452 COVARRUBIAS ET AL.

Table 6. Mass transference parameters for Cr(III) removal from tannery wastewater through
zeolite-packed beds.

Cr3
Kca tb Vb retention
Column %HUNB (min1) (h) (dm3) (mg)

Z13X 52 3.0 2.8 0.84 84

Syn-Mor 43 3.7 4.0 1.20 120
Cudu754  Z13X 25 6.2 7.6 2.28 228
Cudu754  Syn-Mor 40 3.9 7.9 2.37 237
Cudu1865  Syn-Mor 35 4.7 10.3 3.09 309

[Cr]f : 100 mg  dm3; f: 300 cm3  h1; dp: 0.2 mm.

al., 1993) and the overall volumetric coefficient (Kca),
which describes the mass transfer process in the zeolite
bed (Geankoplis, 1993), were calculated from break-
through curves according to procedure described in pre-
vious work (Covarrubias et al., 2005). Kca and %HUNB
are defined as follows:
Nu
Kca  o
Ht
of transfer resistances imposed by the higher quantity of
chromium precipitated on Syn-Mor zeolite bed.
The Cr(III) removal from a diluted tannery effluent
(100 mg Cr3  dm3) through the zeolite packed beds
(dp  0.2 mm) was also evaluated (Fig. 6). In this case,
a hybrid adsorption–ion exchange system consisting of
an activated carbon column (Cudu754, Sg  754 m2 
(1) g1) previously in series connected to zeolite column was
also used. Previous research has shown that the addition

 
t of an activated carbon column is efficient at protecting
%HUNB  1  u 100 (2)
tt the zeolite column from existing dissolved organic mat-
ter in the industrial effluent (Covarrubias et al., 2005).
where N is the overall number of transfer units, Ht is the
From Fig. 6 it can be observed that chromium removal
bed length and uo is the superficial velocity of the fluid.
efficiencies of both Z13X and Syn-Mor zeolite columns
The overall number of transfer units may be obtained
are considerably decreased in the real effluent matrix
graphically by plotting C/Co vs. N(  1), where N( 
(quantitative information is shown in Table 6). The more
1)  1  lnC/Co.  is a dimensionless time (Covarrubias
distorted shape of the breakthrough curves is typical of
et al., 2005). tu is the time equivalent to usable capacity
those obtained in a more complex aqueous matrix, like
of the bed, and tt the total stoichiometric capacity of the
that of the industrial wastewater, where Cr(III) exchange
column if the entire bed reaches equilibrium, which are
process is affected by interfering organics and compet-
provided by a mass balance in the column (Geankoplis,
ing cations existing in the effluent. When the diluted tan-
1993).
Comparing the performance of breakthrough curves, it
can be observed that when the system operates with
smaller particle size, the fraction of unused bed is mini-
mized and the Kca values are increased. These results are
in agreement with the predominant intraparticle diffu-
sional control observed for Cr(III) exchange process in
FAU-type zeolites (Covarrubias et al., 2005; Gazola et
al., 2006), which also indicate that operating with smaller
particle size, the mass transfer resistances are minimized.
Quantitative analysis of the chromium removal through
the columns at the breakthrough time (tb) (Table 5),
confirms higher chromium retention on the Syn-Mor
columns. Although Syn-Mor columns exhibit higher
chromium retention values than Z13X columns, Syn-Mor
columns also present higher mass transfer resistances Figure 7. COD breakthrough curves on activated carbon
(%HUNB and Kca values), which can be the consequence columns (f : 300 cm3  h1, dp: 0.2 mm).
ZEOLITES FOR CHROMIUM REMOVAL FROM WASTEWATERS
nery effluent was first passed through a column filled
with activated carbon and thereafter through the column
filled with zeolite (cudu  zeolite system), Cr retention
was increased about factor 2.71 for Z13X column and
about factor 1.97 for Syn-Mor column. In addition, the
percentage of unused bed is reduced and the Kca values
are increased, which indicates an improvement in the
mass transfer conditions during dynamic ion exchange
process. When an activated carbon of higher specific
surface area was used (Sg  1,865 m2  g1), both the
chromium removal efficiency and the mass transfer con-
ditions were improved in the operation of Syn-Mor col-
umn. In order to verify the effect of activated carbon on
zeolite column performance, chemical oxygen demand
(COD) breakthrough curves were obtained at the outlet
of the activated carbon column. From Fig. 7 it can be ob-
served that the activated carbon column produces an im-
portant reduction in the COD of the effluent, which in-
creases with the specific surface area of the activated
carbon. Thus, the increasing in chromium removal by us-
ing the activated carbon  zeolite column system is
mainly due to the adsorption of organic matter onto the
activated carbon column, and to lesser degree, to the re-
tention of chromium and competing ions, as has already
been found in the previous study with the commercial
13X zeolite (Covarrubias et al., 2005). This interpreta-
tion postulates that the effluent enters the zeolite column
with low concentrations of organic matter, chromium,
and interfering ions, which prevents the obstruction of
pores and cationic exchange sites in the zeolite, favoring
the Cr(III) exchange in the zeolite column. These results
demonstrate that under the used experimental conditions,
zeolite synthesized from low-cost natural mordenite are
an efficient ion exchanger to be used in conjunction with
activated carbon for Cr(III) removal operations from in-
dustrial tannery effluents.
CONCLUSIONS
The zeolite synthesis from natural mordenite (Syn-
Mor) carried out in a reactor of higher dimensions was
verified. A FAU zeolite-rich product can be obtained un-
der controlled synthesis conditions. The use of silicate-
urea based binders enabled the production of zeolite ex-
trudates with CrEC and compressive strength appropriate
for their use in Cr(III) removal processes from aqueous
solution, these values were as high as those found for
commercial zeolite extrudates. Columns packed with
Syn-Mor zeolite extrudates, exhibited high efficiency in
the removal of Cr(III) from synthetic and diluted tannery
wastewater. Thus, synthesis of zeolites from natural mor-
denite and their subsequent forming process appear as a
1453
feasible and promising alternative to produce an efficient
ion exchanger for tannery wastewater treatment.
ACKNOWLEDGMENTS
The authors wish to thank CONICYT for Doctoral
fellowship (C.Covarrubias) and the MECESUP-red
UCH0116 Project for financial support in X-ray analysis.
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