Removal of Mn(II), Ni(II) and Cu(II) Ions from White

Wine through Ion Exchange in Microporous

Mordenite and Mesoporous Al-MCM-41

CAMELIA ELENA LUCHIAN1, VALERIU V. COTEA2, ION SANDU3*, VIOLETA ELENA COPCIA 1, NICOLAE BILBA1
1
”Al. I. Cuza” University, Faculty of Chemistry, Laboratory of Materials Chemistry, 11 Carol I Bd., 700506 Iasi, Romania
2
University of Agricultural Sciences and Veterinary Medicine 3, Mihail Sadoveanu Alley, Iaºi, 700490, Romania
3
”Al. I. Cuza” University, Scientific Platform ARHEOINVEST, 11 Carol I Bd., 700506 Iasi, Romania

The application of ion exchange microporous (mordenite) and mesoporous Al-MCM-41 molecular sieve to
the metal ions K(I), Fe(II), Mn(II), Ni(II) and Cu(II) removal, of white wine has been studied. The experimental
results demonstrate that ion exchange is effective for metal ions removal and the materials used do not
modify the qualities of the wine. The ion exchange capacity of these materials is not entirely available for
metal ions retaining and on the negatively charged surface the policondensation of small proteins takes
place.
Keywards: wine, Al-MCM-41, mordenite, ion-exchange

Browning and lack of color quality are the main
problems occurring during wine storage and greatly
affect wine quality.
It has been known [1, 2] for many years that the
phenomenon of browning is due to the oxidation of the
polyphenolic compounds present in the wine. The first
step of this process is the oxidation of phenols to
quinones by a nonenzymatic chemical reaction
catalyzed by metals like copper(II) and iron(II, III) [2]
or an enzymatic reaction with the intervention of
polyphenol oxidase [3]. The nonenzymatic chemical
reaction is predominant in wines because the polyphenol
oxidase activity, initially present in the must, diminishes
during fermentation [4]. Besides, the polyphenol oxidase
enzyme is able to catalyze the oxidation of phenols to
quinones but polymerization reactions are nonenzymatic.
These alterations in the organoleptic properties lead to
the rejection of the wine affected, which causes not only
ûnancial loss but also loss of consumer confidence in wine.
The metallic content of a white wine appears to play an
important role in its browning [5].
Iron is very widespread in the earth’s crust (O, Si, Al, Fe
etc.), representing a little over 5% of total mass. It is soluble
in the form of ferrous and ferric salts. Both forms occur in
wine, maintaining an oxidation–reduction balance
according to the electro-active redox system below:
The iron(II) content in commercial wine has to be in the
range of 0.5-5 mg/L, in accordance with European Union
Legislation, but for the house wine it could reach 20mg/L
[6].
Producing wineries have for many years been trying to
reduce metallic content by adding various substances to
the wine. Notable among these is the use of potassium
hexacyanoferrate (II) which causes the elimination of part
of the iron content, together with significant reductions in
the content of other metals that also participate in the
browning and are highly contaminating (Mn, Cu, Zn etc.)
[7]. The use of this complexing agent carries with it the
risk of the possible transformation of the excess quantity
into hydrocyanic, a highly toxic compound [8] as well as
the production of residuals without utility. In recent years,
the search has begun for alternative methods that enable
the metallic content of the wine to be reduced without
altering its composition [9-13].
Ordered mesoporous silica and aluminosilica of the
M41S family, first synthesized 1992 [14] have important
technological applications as size selective adsorbents
sieves, ion exchange, supports for catalysts or as nanoscale
reactors [15].
Among the members of M41S family of materials, the
so-called MCM-41 have been most widely studied, mainly
because of its pseudo-crystalline and textural properties,
such as the hexagonal arrangement of one-dimensional
channels [14] with a sharp pore –size distribution and large
specific surface area [16].
Introduction of foreign ions, for instance, aluminum ions,
into the silicate framework has been proved to be an
efficient route for modifying the surface acidity of Si-MCM-
41 [17]. Bronsted acidity of Si-MCM-41 could be enhanced
significantly after modification with aluminum ions [17].
The Bronsted acidity of aluminosilicates generally arises
from the presence of accessible hydroxyl groups or in the
form of ‘‘bridging’’ Si-(OH)-Al hydroxyl groups (structural
hydroxyls) associated with 4-coordination framework
aluminum. Mesoporous material Al-MCM-41 can be used
as acid catalyst and as ionic exchanger [18].
Mordenite is a mineral or synthetic zeolite with the
chemical formula:
Natural mordenite has the Si / Al ratio ranging between
4.2 - 5.9. This ratio leads to a high thermal and chemical
stability. The structure after dehydration is stable up to 900oC
[19].

* email: sandu_i03@yahoo.com

782 http://www.revistadechimie.ro REV. CHIM. (Bucharest) ♦ 62♦ No. 8 ♦ 2011

 Mordenite in the H+ form is used in heterogeneous Ionic exchange procedure
catalysis, selective adsorption and ion exchange. Ionic exchange experiments were carried out by
Adsorption properties of mordenite are between zeolite shaking increased amounts of Al-MCM-41 and mordenite
LTA and faujasite LTX and its stability depending on the pH powder with 50 mL of wine for 24 h at 5oC. After filtration,
of the solutions exchange, is unchanged [20]. the metal ions concentration in the liquid phase was
In this paper is presented the impact of microporous analyzed spectrophotometrically with AAS spectro-
mordenite and mesoporous Al-MCM-41 material on metal photometer using the OIV methods [23].
ions from white wine.
Results and discussions
Materials and method X-ray Powder Diffraction Analysis (XRPD)
Chemicals Figure 1 shows the small-angle XRPD pattern of the
Tetraethylorthosilicate (TEOS, 98% Merck) as silica calcined Al-MCM-41. It can be seen that Al-MCM-41 sample
source, cetyltrimethylammonium bromide (C 16 H 33 give only one characteristic peak (broader and less intense)
(CH 3) 3 N + Br, Aldrich) as structure directing agent, at the small-angle region corresponding to the (100)
tetraethylammonium hydroxide ((C 2H 5) 4NOH, 10% reflection. This fact indicates a degree of loss of the typical
aqueous solution, Merck) as mineralizing agent, aluminum hexagonal order observed for Si-MCM-41 [21]. The structure
isopropoxide (Al–[O–CH–(CH3)2]3, Merck) as aluminium of Al-MCM-41 is less ordered than the well ordered structure
source and demonized water were used as received in the of Si-MCM-41; probably, a dealumination process takes
synthesis of Al-MCM-41. place during the template removal by calcination [21].
The commercial H-mordenite came from Tosoh
Corporation Tokyo, Japan.
A bottled wine (Feteascã Albã) originated from Iasi area
(Romania) and winified in 2009 was selected for the
experiments.
Synthesis of Al-MCM-41
For the synthesis of Al-MCM-41 (Si/Al = 16) material,
22.3 mL (1 mol) of tetraethylorthosilicate was mixed with
0.68 g (0.033 mol) of aluminum isopropoxide (dissolved in
5 mL of deionized water). The mixture solution was stirred
for 30 min at a speed of about 250 rpm and tetra-
ethylammonium hydroxide solution (10% water) was
added with continuous stirring for another 30 min at a speed Fig. 1. Small-angle XRPD pattern of mesoporous Al-MCM-41
of about 250 rpm until the gel formation (pH=11). After
that, 7.2 g (0.2 mol) of cetyltrimethylammonium bromide
was added dropwise (30 mL/h) so that the gel changed N2 physical adsorption-desorption
into suspension. After further stirring for 1 h, the resulting
gels of composition:
1SiO2 : 0.033Al2O3 : 0.2C16TMABr : 100H2O,

was transferred into a teflon-line steel autoclave and heated

to 150oC for 48 h. After cooling, the solid was recovered by
filtration, washed with deionized water and ethanol, dried
in air at 100oC for 1 h and finally calcined in flowing air at
540oC for 6 h [17].

Characterization
X-ray diffraction. The small-angle XRPD pattern of the
calcined powder was performed using a PANalytical X’Pert
PRO MPD diffractometer using Ni filtered CuKα radiation
(λ = 0.15406 nm). The data were collected with 2θ
varying from 0.5 to 7o at room temperature.
N2 sorption. The nitrogen adsorption – desorption isotherm
at -196oC was determined on a NOVA 2200 Quantachrome
sorption apparatus. Prior to the adsorption measurement
the sample was outgassed under vacuum for 3 h at 300oC.
The BET surface area was calculated based on the
adsorption data in the relative partial pressure range of
0.05-0.25. The pore size distribution was calculated from
the nitrogen adsorption isotherm using the Barrett-Joyner-
Halenda (BJH) method [21].
The metallic content was analyzed spectrophoto-
metrically with an atomic absorption spectrophotometer
ContrAA 300, Analitik Jena.

Fig. 2. The N2 adsorption-desorption isotherm (a) and pore size

distribution (b)of AlMCM-41
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a
Fig. 3. Mn(II) removing with sorbents doses(a) and efficiency % (b).
The N2 adsorption-desorption isotherm and the pore size
distribution calculated by BJH method of the synthesized
Al-MCM-41 are shown in figure 2.
The isotherm can be classified as type IV; the absence
of the sudden steep increase between a relative pressure
p/po = 0.25-0.45 is an indication that the mesopores
associated with the capillary condensation have a large
distribution in size.
The BET surface area, average pore diameter and pore
volume of the Al-MCM-41 material were found to be 685
m2/g, 2.8 nm and 0.69 cm3/g (at p/po = 0.97), respectively;
the pore wall thickness calculated by the difference
between the lattice parameter ao and the pore size has a
value of 2.15 nm. The incorporation of aluminum in Si-
MCM-41 structure leads to a decrease of BET surface area
and pore size and an increase of pore wall thickness.
Standard chemical analysis of wine
Total acidity, ethanol, pH, volatile acidity, total and free
SO2, sugars and total dry mater (TDM) of the used wine
were analyzed according to the methods proposed by O.I.V.
(2006) [22] (table 1).
784 http://www.revistadechimie.ro
Table1
PHYSICO- CHEMICAL CHARACTERISTICS
OF WHITE WINE (FETEASCA ALBA)
Table 2
INSTRUMENTAL PARAMETERS
Table 3
DISTRIBUTION OF Mn(II) BETWEEN WINE
AND MICROPOROUS MORDENITE AND
MESOPOROUS Al-MCM-41
b
Retention of Mn(II), Ni(II), Cu(II) by ion exchange onto Al-
MCM-41 and mordenite
The values of the working parameters of the AAS
method are presented in table 2. The calibration of the
spectrophotometer was done with Merck standard
solutions.
In order to establish the content of Mn(II), Ni(II), Cu(II),
the samples of wine after ion exchange were directly
absorbed in the flame of the device without mineralization
[24].
The content of Mn(II), Ni(II) and Cu(II), was
simultaneously analyzed coresponding to each set of
sample.
These materials (Al-MCM-41 and mordenite) have never
been used until now in the wine treatment processes.
The distribution of Mn(II), Ni(II) and Cu(II) between wine
and ion exchangers are presented in tables 3-5 and figures
3-5.
From table 3 it is noted that both materials used are
effective in retaining Mn(II).
Increasing the dose levels of AL-MCM-41 and mordenite
from 1 to about 5 g/L wine, the content of Mn(II) in wine
REV. CHIM. (Bucharest) ♦ 62♦ No. 8 ♦ 2011
 Table 4
DISTRIBUTION OF Ni(II) BETWEEN
WINE AND MICROPOROUS
MORDENITE AND MESOPOROUS Al-
MCM-41

Fig. 4. Ni(II) removing with

sorbents doses(a) and
efficiency % (b)

b
a

Table 5
DISTRIBUTION OF Cu(II) BETWEEN
WINE AND MICROPOROUS MORDENITE
AND MESOPOROUS Al-MCM-41

Fig. 5. Cu(II) removing with

sorbents doses(a) and
efficiency % (b)

a b

decreases and the degree of Mn(II) retention increases to
25 and 26,29% respectively.
Variation of retained manganese concentration with
adsorbents doses and efficiency in manganese removal is
shown in figure 3.
From table 4 it is noted that both materials used are
effective in retaining Ni(II).
Increasing the dose levels of AL-MCM-41 and mordenite
from 1 to about 5 g/L wine, the content of Ni(II) in wine
decreases and the degree of Ni(II) retention increases to
53.6% and 65.97% respectively.
Variation of retained nickel concentration on mordenite
and Al-MCM-41 doses is shown in figure 4.
From table 5 it is noted that both materials used are
effective in retaining Cu(II).
REV. CHIM. (Bucharest) ♦ 62♦ No. 8 ♦ 2011 http://www.revistadechimie.ro
Increasing the dose levels of AL-MCM-41 and mordenite
from 1 to about 5 g / L wine, the content of Cu(II) in wine
decreases and the degree of Cu(II) retention increases to
72.2 and 62.27% respectively.
Conclusions
The benefits of the use of Al-MCM-41 mesoporous and
mordenite nicroporous molecular sieve as sorbents in the
treatment of white wine mainly consist in a significant
decrease of Mn(II), Ni(II), Cu(II) content.
The ions removing efficiency of Mn(II), Ni(II), Cu(II) from
white wine on Al-MCM-41 and mordenite corresponds to
the values 25, 53.6, 72.02 and 26.29, 65.97, 62.27%
respectively.
Both sorbents act as ion exchanger and selective
adsorbent for small proteins.
785
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Manuscript received: 24.05.2011
REV. CHIM. (Bucharest) ♦ 62♦ No. 8 ♦ 2011