This section may be divided by subheadings. It should provide a concise and precise description of the experimental results, their interpretation, as well as the experimental conclusions that can be drawn.
3.2. Adsoption study
Study of sorption characteristics of modified bentonite-based sorbents. An important characteristic in the study of the adsorption process is the kinetics of adsorption, which is necessary to determine the time of the establishment of adsorption equilibrium when removing adsorption isotherms. Nickel (II) cations were selected as testing metal cations in the study of the adsorption process by modified sorbents based on the studied bentonites obtained by the "co-precipitation" method. The sorption experiment technique was as follows: the samples of sorbents weighing 1-2 g were filled with distilled water for 1 hour, then the water was decanted and 100 ml of a model solution of nickel (II) sulfate of a certain concentration was poured, and the adsorbent was mixed with the model solution. Then samples were taken from the middle layers of the solution through 5, 10, 15, 20, 30, 60, 120, and 180 minutes. Quantitative analysis of the sample for the content of nickel cations was performed on an energy–dispersive X-ray fluorescence spectrometer EDX-720 by the method of calibration curves. Data on the kinetics of adsorption of nickel (II) cations on the studied sorbents, obtained based onbentonite from the Dash-Salakhli deposit, are shown in
Figure 2. Analysis of kinetic data on the sorption of nickel (II) cations on the studied sorbents indicates that the saturation of sorbents with cations under these conditions has been occurring for 2hours. Therefore, in the future, when removing the sorption isotherms, the time for establishing the adsorption equilibrium was 2 hours.
The method of removing the adsorption isotherms of nickel cations on the studied sorbents was as follows: as in kinetic experiments, the samples of the studied sorbents weighing 1-2 g were filled with distilled water for 1 hour, then the water was decanted, and filled with 100 ml of a model solution of nickel sulfate of various concentrations (100, 200, 300, 400 and 500 mg / l), were kept for 2 hours until the equilibrium concentration in the solution was reached. The samples were taken from the middle layers of the solution. Quantitative analysis of the elemental composition of the sample was also performed on an energy–dispersive X-ray fluorescence spectrometer EDX-720 using calibration curves.
According to the average values of equilibrium concentrations (at least two parallel measurements), the adsorption value was calculated using the following formula (1):
А– adsorption capacity of the sorbent, mg/g;
Сi – initial concentration of the studied ions in solution, mg/l;
Сe – equilibrium concentration of the studied ions in solution, mg/l;
V– volume of the test solution, l;
m– the mass of the sorbent taken for analysis, g.
Figure 3 (a, b) show the adsorption isotherms of nickel (II) cations on the studied sorbents obtained on the basis of natural bentonites of the mod.1 and mod.2 deposits. Ranges of different concentrations show the true picture of the surface [
16]. All the obtained isotherms belong to Langmuir-type (L-type) isotherms [
17]. The Langmuir adsorption isotherm equation, derived based on molecular kinetic theory and ideas about the monomolecular nature of the adsorption process, when applied to solutions has the form of equation (2):
Where, K is the adsorption equilibrium constant characterizing the adsorption energy;
С – equilibrium concentration, mg/l;
А∞ – the maximum adsorption value, (monolayer capacity), mg/g.
An adsorption isotherm is a good tool for understanding the nature of the sorbent surface. The Langmuir adsorption isotherm (2) is linearized in coordinates 1/A = f (1/С), which allows graphoanalytically determining the values of the coefficients K and A∞. The obtained adsorption isotherms were processed in accordance with the Langmuir equation in inverse coordinates according to equation (3):
Figure 4 (a, b) show the adsorption isotherms of nickel (II) cations for the studied sorbents in inverse coordinates in accordance with equation (3).
Figure 3.
(a, b) Isotherms of adsorption of nickel (II) cations in a neutral medium.
Figure 3.
(a, b) Isotherms of adsorption of nickel (II) cations in a neutral medium.
The results of adsorption studies are presented in
Table 3.
The obtained values of the maximum adsorption capacity with respect to nickel cations are generally consistent with the data on the total specific surface area of these sorbents. For samples with a high specific surface area, the absorption of the studied cations from model solutions is greater than for samples with a low specific surface area. The observed increase in the adsorption of nickel cations on Fe- and Al-modified sorbents compared to natural bentonites can also be explained by the fact that, along with the formation of a layered-columnar structure leading to an increase in the specific surface area, modification also leads to an increase in the number of Al-OH and Fe-OH anion exchange centers [
14,
18].
Establishing the mechanism of the adsorption process on natural bentonite and sorbents based on it is difficult to describe, because the adsorption process on bentonite clays can be carried out simultaneously by several mechanisms with the predominance of one. Adsorption processes carried out by montmorillonites occur mainly by three mechanisms:
a) by the type of ion exchange.
b) by the formation of chelate complexes with surface hydroxogroups of the mineral.
c) with the help of valence "broken" bonds at the edges and corners, at the shear growth stages of montmorillonite crystals.
The most well-known mechanism is ion exchange. Ion exchange has a fundamental and practical application for all bentonite clays. It is known that the source of bentonitecation exchange ability is interlayer cations of sodium, lithium, calcium, potassium, and magnesium, which compensate for the negative charge of montmorillonite layers. As a result of this mechanism, interlayer cations are exchanged for adsorbent cations (heavy metals) that are in water.
In addition, heavy metal ions can be deposited on the surface in the form of (hydra) oxides, hydroxocarbonates or other basic salts.
Most authors interpret the mechanism of adsorption on natural clay minerals of aluminosilicate composition as ion exchange [
18,
19]. But based on the data we have obtained; it follows that the mechanism of adsorption on bentonite clays is complex. The main process is ion exchange, which can be either cation exchange or anion exchange. The higher sorption activity of the studied Al-modified bentonites in comparison with Fe-modified ones is determined by the high content of Al-OH anion exchange centresin them, which can also take part in the processes of complexation.