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Article

Adsorption of Vanadium (V) on Amorphous and Modified Silica

by
Olga A. Timoshchik
1,*,
Tatiana D. Batueva
2,
Elena A. Belogurova
1 and
Alexander G. Kasikov
1
1
Tananaev Institute of Chemistry—Subdivision of the Federal Research Centre “Kola Science Centre of the Russian Academy of Sciences”, 184209 Apatity, Russia
2
Institute of Technical Chemistry of the Ural Branch of the Russian Academy of Sciences—A Branch of the Perm Federal Research Centre, 614013 Perm, Russia
*
Author to whom correspondence should be addressed.
Water 2024, 16(24), 3628; https://doi.org/10.3390/w16243628
Submission received: 21 November 2024 / Revised: 10 December 2024 / Accepted: 13 December 2024 / Published: 17 December 2024
(This article belongs to the Section Wastewater Treatment and Reuse)
Browse Figures
Figure 1
<p>The pore distribution of the samples as a function of the specific surface value of SiO<sub>2</sub>.</p> "> Figure 2
<p>Structure of sorbents before (<b>a</b>) and after (<b>b</b>) surface modification with N′,N′-dimethylhydrazides.</p> "> Figure 3
<p>Low-temperature adsorption isotherms of nitrogen for the original (1) and modified (2) sorbents.</p> "> Figure 4
<p>Integral (black line) and differential (blue line) curves of the pore size distribution for the original (<b>a</b>) and the modified sorbent (<b>b</b>) I+DMHD (IV).</p> "> Figure 5
<p>Sorption capacity of sorbents to ions V(V) in relation to pH (mSiO<sub>2</sub> = 0.02 g, C(V) = 0.001 mol/L, τ = 20 min).</p> "> Figure 6
<p>The dependence of the kinetic curve of adsorption of V(V) by sorbent IV at 20 °C on time (<b>a</b>), and the time dependence of the degree of completion of the adsorption process of V(V) by sorbent IV at 20 °C (<b>b</b>).</p> "> Figure 7
<p>Dependencies −ln(1 − <span class="html-italic">F</span>) on time t (<b>a</b>) and F on t<sup>1/2</sup> (<b>b</b>) in the sorption of V(V) ions on sorbent IV.</p> "> Figure 8
<p>Kinetic curves of vanadium sorption: (<b>a</b>) pseudo-first-order and (<b>b</b>) pseudo-second-order.</p> ">
Review Reports Versions Notes

Abstract

:
In this work, we investigate V(V) sorption on amorphous and modified silica. Silicon dioxide was obtained from the metallurgical slag. The impact of modification on vanadium sorption was studied. The surface was modified with hydrazides (HDs) and dimethylhydrazides (DMHDs) of the tertiary carbonic Versatic acids CH3R1R2CC(O)OH of the C10–19 fractions. The optimal sorption conditions on the unmodified sorbent were pH 4, 1 h, and 40 °C. The sorption capacity of V(V) ions increased with surface modification. For modified sorbents, the range of action shifted to a more acidic area (2.0–3.0), where the HV10O285− polyanion formed a complex with N′,N′-dimethylhydrazide groups. When studying the kinetics of the V(V) sorption process on silica samples, the optimum time of adsorption equilibrium establishment (10 min) and reaction mechanism were determined. The sorption process was significantly accelerated by surface modification. The vanadium sorption process is described by pseudo-second-order kinetics. The study of adsorption isotherms revealed that the vanadium sorption isotherm corresponds to the Langmuir equation. The differences in the extraction of vanadium ions are explained by different sorption mechanisms, which are associated with the variety of vanadium forms in the solution.

1. Introduction

Vanadium is a rare but vital metal for various industries. Vanadium reserves around the world add up to about 38 million tons (China, Russia, and South Africa are the leaders in terms of these reserves) [1]. It is a significant metal for metallurgy in, for example, the production of alloys, aviation, space and nuclear engineering, catalysts, drugs, ceramics, and redox batteries [1,2,3,4,5,6,7]. The necessity of vanadium increases yearly; hence, the amount of vanadium-containing waste increases. Compounds of vanadium are toxic. Vanadium is a redox-sensitive element: at a pH close to neutral, V(IV) oxidizes to V(V). This is the most harmful and mobile form of vanadium [8].
Vanadium content (for oxide) in production wastes can exceed its content in natural raw materials by 10–100 times [9]. The storage of vanadium-containing waste is hazardous to the environment because it contaminates surface water, groundwater, and soils. The solubility of vanadium in waste is affected by the pH and redox conditions of the area [8]. Vanadium leaching occurs at low and high pH values (<4, >8) due to pH-dependent differences in sorption affinity. In Russia, according to drinking water requirements, the concentration of vanadium should not exceed 0.1 mg/L, and for fishery bodies of water, it should not exceed 0.001 mg/L.
Spent vanadium catalysts are one such waste product [10,11]. Vanadium catalysts are used in the chemical and oil industries because they are cheap and resistant to various substances. They all contain vanadium, but coal ash contains less than oil ash [5,12]. All of them contain vanadium, but coal ash contains less of it than oil ash. When fuel oil is burned, about 90% of the vanadium enters the air in the smoke. Vanadium enters the atmosphere by precipitation and ends up in soil and water bodies, thus influencing biological cycles. Wastewater has a high vanadium content, which can cause detrimental effects on people, animals, and plants. Therefore, the removal of vanadium from wastewater is of great importance.
Plants from the soil absorb vanadium. In small amounts, it promotes their growth, but in excess, it leads to reduced growth [13]. Excess vanadium in the human body can cause anemia, cough, emaciation, mucous membrane irritation, gastrointestinal disturbances, and bronchopneumonia [12].
There are many ways to remove vanadium from aqueous systems: adsorption, chemical precipitation, solvent extraction, electrokinetic remediation, photocatalysis reduction, coagulation, microbiological treatment, and membrane filtration methods [14,15,16]. The high reactivity of vanadium causes complexity in its chemical behavior. In aqueous solutions that are formed during the processing of technological products, vanadium exists at higher oxidation degrees, and forms vanadate, hydrolyzed compounds, and heteropolycompounds whose compositions are determined by the specific conditions of the process behavior [13,15]. There are 12 forms of vanadium in aqueous solutions, which can be divided into cationic [VO2+], neutral [VO(OH)3], and anionic V10O26(OH)24−. In addition, there are mono- or polyvanadate VO2(OH)2−, VO3(OH)2−, VO43−, V2O6(OH)3−, V2O74−, V3O93−, V4O124− [17,18].
Extraction is a common way to extract vanadium from various aqueous solutions. Vanadium can be extracted from sulfuric acid, nitric acid, and fluoride solutions, but in hydrochloric acid solutions, V(V) is partially reduced to V(IV). Cation exchange, neutral, and anion exchange extractants can be used for extraction [19,20,21,22].
Sorption is one of the most effective technologies [23,24]. To extract V from different solutions, for example, industrial effluents use various materials such as exchange resin, cellulose-based fiber anion exchangers, and inorganic adsorbents [6,14,15,16,17,18,25,26,27,28,29,30,31,32].
However, vanadium cannot be removed from solutions using activated carbon [30]. Using melamine as a sorbent, vanadium recovery up to 99.97% at pH 1.18 can be achieved within an hour. The adsorption kinetic data correspond to the pseudo-second-order [6]. The sorption of vanadium on T A-62(MP) (Thermax Ltd., India)ion exchange resin reaches values of 97.5–99.9% within 3 h at pH values of 6.0–7.0 in aqueous medium [14]. In [15], the sorption of vanadium on different anion exchange resins and Lewatit AF5(Lanxess Deutschland) was studied. The optimum pH value was 6.0. From the results, it was found that Purolite S984 (Purolite, Great Britain) could recover vanadium from wastewater by 98%, Purolite A830 (Purolite, Great Britain) by 80.6%, and Purolite A430TL (Purolite, Great Britain) by 67.8%.
Amorphous silica is an attractive material for many industries due to its porosity and high surface area [3]. It can be applied to sorption, catalysis, drugs, and others [33,34]. The use of nanoparticles significantly reduces the cost of wastewater treatment processes; they are stable at high temperatures, have high specific surface values, and have high reactivity and selectivity [16]. Surface modification with different reagents leads to the improvement of the sorption properties of the sorbent [7,25,26]. The presence of functional groups and mesopores is the reason for improving the sorption process. Different organic compounds, inorganic salts, metals, and oxides are used to modify the surface of SiO2.
In recent years, the synthesis, properties, and practical application of hydrazides and N′,N′-dimethylhydrazides based on neocarboxylic acids with the general formula RR′R″CCOOH (radicals R, R′ and R″ are equal to CxH2x+1, and x ≥ 1) have been studied [35]. This method is superior to the prototype—Cyanex 301.
Hydrazine derivatives and neoacids (solutions in kerosene) are effective in the extraction of V(V) [36]. The extraction proceeds by anion exchange and addition mechanisms. The recovery of vanadium from sulfuric acid and hydrochloric acid solutions using these reagents is high at pH values of 2.5–3.5.
The use of hydrazides (HD) and dimethylhydrazides (DMHD) to modify a silica surface with high textural characteristics will make it possible to concentrate microcomponents from large volumes of solutions on a relatively small mass of sorbent without using organic solvents.
Slags are industrial waste containing heavy metals that are released over time. Therefore, recycling them to obtain valuable components is an extremely important task. Silicon dioxide is one of the substances obtained from slag processing.
MCM-48 and MCM-41 have been synthesized previously. Their modification with hydrazides and dimethylhydrazides was carried out. Sorption of molybdenum, tungsten and non-ferrous metals was studied on the obtained sorbents [37,38]. The possibility of the separation of tungsten and molybdenum from hydrochloric acid solutions of 3 mol/L concentration with a pH of 1.5 was established [37]. Hydrazide- and dimethylhydrazide-modified MCM-48 was also used for the sorption of non-ferrous metals. The highest degree of extraction (80–90%) of the three nonferrous metals was reached in a neutral and an alkaline medium by the sorbent modified with amide groups via hydrothermal synthesis. In the pH range, 1.5–6.0 cobalt can be separate from nickel and copper [38]. SiO2 obtained from metallurgical slags was modified by TOPO. The physicochemical properties of the sorbent were studied, and the sorption of rhenium from sulfuric acid solutions was investigated. It was found that this sorbent can withstand up to 20 cycles of sorption–desorption. Moreover, the extraction of rhenium from industrial sulfuric acid solution allows up to 99% of it to be extracted, and allows it to be separated from other elements [39].
Therefore, the aim of this work was to study the process of the sorption of V(V) from solutions on amorphous silica obtained during the processing of copper–nickel slags and modified with hydrazide and dimethylhydrazide groups.

2. Materials and Methods

2.1. Materials

All the reagents employed in the experiments were of analytical reagent grade. The silica samples were obtained from Kola Mining–Metallurgical Company (Kola MMC’ Nornickel, Kola Peninsula, Russia) metallurgical slag, and contained up to 99% SiO2 content [40]. Hydrazides and dimethylhydrazides were prepared from Versatic 10 acids (CH3R1R2CC(O)OH tertcarboxylic acids, where R1 and R2 are alkyl radicals in which the number of carbon atoms is 10 and 1519, respectively) at the Institute of Technical Chemistry of the Ural Branch of the Russian Academy of Sciences—a branch of the Perm Federal Research Center.

2.2. Characterization Methods

The textural parameters of the sorbents (specific surface area, total pore volume, pore diameter, and pore size distribution) were determined with low-temperature nitrogen sorption at −196 °C on the ASAP 2020 device (Micrometrics, Norcross, GA, USA) after degassing the material under a vacuum at 90 °C for 180 min. The surface modification was confirmed by IR spectroscopy in the area of 150–4000 cm−1 on an IFS-66/S FTIR spectrometer (Bruker, Germany). Electron microscopy was used to obtain information about the structures of the synthesized sorbents (FEIQuanta 650FEA, Hillsboro, OR, USA).

2.3. Preparation of Adsorbents

For silica samples with different surface characteristics, the following method was used [40]. Kola MMC’s slag was leached with 10% sulfuric acid at a slag:acid ratio of 1:10 at 20 °C for 60 min. The leaching solution was used to extract SiO2. The solution was dried, the mixture was washed with hot distilled water to separate the SiO2 and a mixture of FeSO4 and MgSO4, and it was dried to a constant mass (Sample 4 in Table 1).
Some silica-containing powders were dissolved in 2N NaOH at 20 °C for 60–120 min to obtain Na2SiO3 solutions. A sodium silicate solution was obtained by dissolving silica residue after sulfur acid leaching (impurities < 10−3 g/L). Sulfuric acid was used to bring the solution to pH 2 or 7 to obtain silica with different characteristics. The obtained precipitate was separated from the mother liquor by filtration, washed with distilled water, and dried to a constant weight at 100 °C. The effects of sludge concentration, temperature, process duration, sludge pH, and residence time have been studied previously (Sample 1–3 in Table 1) [41].
The impregnation method was used to modify the silica surface [42]. Silica-based:modifier ratios of 1:0.1 and 1:0.01 were used, with different modification times and temperature regimes. A sample of silica was placed in a round-bottom flask, an estimated amount of N′,N′-dimethylhydrazide (DMHD) or hydrazide (HD) was added, and the mixture was refluxed in ethanol for 300 min. The reaction mixture was filtered, and the solid residue was dried at 70 °C to remove the solvent.

2.4. Experiment Methodology

The sorption properties of the samples were investigated under static conditions. Sorption was performed from aqueous solutions obtained by dissolving the required NH4VO3 portions. The solutions were adjusted to the desired pH value using 1% NH4OH solution and 14% H2SO4.
V(V) solution with a salt content of 0.0229 M was placed in a 10 mL flask. Then, 0.020–0.025 g of sorbent was added, and the solution was shaken thoroughly, after which it was kept for 20 min. At the end of the sorption process, the solutions were separated from the solid phase by filtration through a paper filter.
The following sorption parameters were studied: pH (2–9), contact time (10–60 min), effect of the specific surface area of silica, and process temperature (20–60 °C).
The vanadium concentration was determined by the photocolorimetric method. For this purpose, 10 mL of the solution obtained after sorption was retrieved, diluted with 2N HCl to 45 mL, and 1 mL of 3% H2O2 was added, and it was brought to 50 mL with water. The solution was stained orange due to the formation of the complex ion [V(O2)]3+. The measurement was performed at λ = 450 nm.

2.5. Adsorption Isotherms

The solution with a V(V) content ranging from 3.06 to 10.188 g/L was used to plot the adsorption isotherm. Adsorption was performed at 20 °C for 40 min. The value of the static sorption capacity by the metal (EM) and the degree of extraction (E) were calculated similarly [42].
To determine the limiting stage of the adsorption process, we used a graph-analytical method to analyze the dependence of the degree of completion of the adsorption process (F) on the adsorption time (t) [43]. The degree of completion of the process F was calculated by Equation (1):
F = A t A m a x ,
where Amax is the value of the limiting adsorption, and At is the current value of adsorption.
For external diffusion processes, the kinetic Equation (2) is as follows:
ln ⁡ 1 − F = y × t ,
where y is a constant for the given process conditions, and t is the adsorption time.
The amount of adsorbate in the diffusion-controlled process can be expressed by Equation (3) [44]:
A t = k d × t 1 2 ,
where At is the amount of adsorbate per unit adsorbent area, mol/m2; kd is the rate constant of internal diffusion, mol/m2·min1/2; and t is time, min.

3. Results and Discussion

3.1. Study of the Sorption Process on SiO2

3.1.1. Specific Surface Area Effect

The specific surface area of silica is related to particle size. Thus, samples with a high specific surface area have a small pore size, and samples with a low specific surface area have a larger pore size. Figure 1 shows the pore distribution of silica particles with high, medium, and low specific surface areas. In addition, the pore size can be used to determine the silica. Since the particles have a size range of 2–50 nm, these samples are mesoporous, and samples with a high specific surface area can be classified as microporous.
A study of vanadium sorption on silica on different surfaces was carried out under the following conditions: initial concentration of V(V) = 1 g/L, T = 20 °C, τ = 30 min, sorbent:volume ratio = 1:50, and pH = 7. Samples with a high specific surface area had greater visibility (EM = 0.023 mmol/g, compared to 0.009 and 0.011 mmol/g for minimal and medium specific surface areas), so further sorption was carried out on these samples.

3.1.2. Time Effect

A study of the impact of process time found that the maximum degree of extraction was achieved after 1 h (E = 20.2%, EM = 0.006 mmol/g) under the following conditions: initial concentration of V(V) = 1 g/L, T = 20 °C, sorbent:volume ratio = 1:50, and pH = 7. A further decrease may have be due to a decrease in the number of free sorption centers and the stability of the formed sorbent–metal complex in these pH ranges.

3.1.3. pH Effect

The important factor for vanadium sorption is pH. The influence of pH on sorption was studied under the following conditions: initial concentration of V(V) = 1 g/L, T = 20 °C, τ = 60 min, and sorbent:volume ratio = 1:50. The maximum recovery is achieved at pH = 4 (E = 44.13%, EM = 0.019 mmol/g). This is because at pH 4–10, V(V) exists mainly in the form of VO3−, and in solution with silica, it forms an electroneutral complex [30]. This complex promotes the vanadium sorption process on the silica surface, as the anions migrate to the silica surface and exchange surface groups. Because of the competition between OH− and vanadium, the sorption rate is reduced, and an acidic area is more suitable for vanadium sorption [45]. At pH 7, the silica surface is recharged, i.e., the sorbent surface changes its charge from positive to negative. Vanadium in the alkaline region exists in an anionic form, and its particles are repelled from the silica surface [3].

3.1.4. Temperature Effect

The effect of temperature on sorption was studied, under the following conditions: initial concentration of = V (V) 1 g/L, τ = 60 min, sorbent:volume ratio = 1:50, and pH = 4. Maximum recovery was achieved at 40 °C (E = 53.7%, EM = 0.025 mmol/g). At low temperatures, inhibition of silica activity occurs, which can lead to a decrease in adsorption. High temperatures activate the desorption process [3].

3.2. Study of the Sorption Process on Modified SiO2

For the improvement of the silica’s characteristics, the surface was modified with hydrazides (HD) and dimethylhydrazides (DMHD) of the tertiary carbonic Versatic acids CH3R1R2CC(O)OH of the C10–19 fractions.

3.2.1. SEM

Electron microscopy was used to obtain information on the structure of the synthesized sorbents. The modified samples were similar in morphology and appearance. All the synthesized sorbents were white amorphous powders, which are rarely light beige in color (Figure 2).
Surface modification leads to a reduction in the sorbent grains, while the surface area and pore volume are also reduced. The reason for this may be the incorporation of branched dimethylhydrazide groups of Versatic acids into the sorbent walls, and the “popping” of pores during hydrothermal treatment.
The results of the study of the structural features of the silica sorbents modified by functional groups, obtained by FTIR, are summarized in Table 2.
According to the results of the studies carried out by IR spectroscopy, it can be assumed that in the process of modification of the silica base, most likely, the modified silica matrix interacts with the formation of the hydrogen bonds and their associates. This is indicated by the decrease in the intensity of the 3900–2900 cm−1 band.

3.2.2. Adsorption Isotherms Study

Table 3 shows the SiO2 samples used to study the patterns of sorption extraction of V(V) from aqueous solutions.
The SiO2 adsorption isotherm is characterized by a broad section of capillary-condensation hysteresis, indicated by increased steepness at increased relative pressure. Surface modification leads to a narrowing of the hysteresis loop for silica I+DMHD without heating, consistent with a change in pore size (Figure 3).
The typical pore size distribution in the initial SiO2-I sorbent is shown in Figure 4, according to which the predominant pore size is 15–25 nm.
For the modified sorbent IV, the integral and differential curves of the percent distribution of particles by fractions are shown in Figure 4. Based on the obtained graphic dependence, the pore size decreases to 10–20 nm, which agrees with the data in Table 2. Based on the results of the study of the physical and chemical properties of the new sorbents, sample IV was selected for further research. The effect of pH on the sorption of pentavalent vanadium was studied for the unmodified sorbent and for sorbents № II–IV. The results of the studies are shown in Figure 5.
The unmodified silicate sorbent can extract V(V) ions in a wide pH range, but its sorption capacity is relatively low (EM at pH = 5.7 0.19 mmol/g, at pH 7 = 0.024 mmol/g, and at pH 9 = 0.031 mmol/g). Grafting of the functional groups of HD and DMHD improves the properties of the sorbents concerning V(V) ions. The maximum extraction of V(V) on sorbent II was 0.61 mmol/g at pH 3.36; on sorbent III, it was 0.25 mmol/g at pH 4.74; and on sorbent IV, it was 0.25 mmol/g at pH 2.80.
The graphical dependence in Figure 5 shows that during modification, the range of effective sorbent action shifts to the acidic region, where the HV10O285− polyanion binds to the complex with grafted DMHD groups. It is also possible to conclude an influence of the modifier’s concentration on the extraction of metal ions. Changing the matrix–modifier ratios from 1:0.01 to 1:0.1 in acidic areas leads to a significant increase in sorption capacity, while the extraction of vanadium ions also increases.
In the next stage of the study, the kinetics of the proceeding processes were studied, which allowed us to determine the optimal time for the establishment of the adsorption equilibrium and for the mechanisms of the reactions to proceed.
The mechanism of interaction of the substance with the adsorbent was determined by establishing the limiting stage of the sorption process, which proceeds in several stages: external diffusion of the absorbed substance to the adsorbent, and internal diffusion of the adsorbent inside the pores to the active centers of the absorber. In addition, there is condensation of the absorbed substance on the inner pore surface as a result of physical adsorption or chemisorption.
The kinetic curve of the adsorption of vanadium ions by the modified sorbent at the optimal pH value is shown in Figure 6a. It follows that the period of complete vanadium sorption by the modified sorbent was 10 min. With unmodified silica, this time was 60 min. The dependence of the degree of completion of the process on the time of sorption of ions V(V) is shown in Figure 6b.
For the determination of the rate-limiting stage of sorption, the graphoanalytical method of plotting the dependencies −ln(1 − F) = f(t) (external diffusion kinetics) and F = f(t1/2) (intradiffusion kinetics) was used (Figure 7a,b). In these relationships, F is the degree of completion of the process, calculated by the formula F = E/Ee, in which E and Ee are the adsorption values at time t and the equilibrium state.
A comparison of the linear correlation coefficients allowed us to establish the mechanism of interaction. According to the obtained graphical dependencies (Figure 7a), at the initial moment, the adsorption process V(V) was due to the external diffusion of vanadium ions to the sorbent surface (R2 = 0.9911). When establishing the sorption equilibrium, the greatest influence was exerted by intradiffusion processes (Figure 7b) (R2 = 0.9211).
To determine the order of the quasiochemical reaction of the interaction of the modified sorbent with vanadium ions, the data obtained were processed using pseudo-first- and pseudo-second-order kinetic models (Figure 8).
The pseudo-first-order kinetics is described using Lagergren’s equation, which describes the sorption by solid adsorbents from the liquid phase:
lg ⁡ C τ − C e = lg C e − k 1 × τ ,
where Cτ is the current adsorbent concentration, mmol; Ce is the equilibrium adsorbent concentration, mmol; τ is the adsorption time, min; and k1 is the rate constant, min−1.
The pseudo-second order kinetics is described by the classical equation, which, in its integral form, has the following form:
1 C τ = 1 k 2 × C e 2 + τ C e ,
where k2 is the rate constant, (mmol·min)−1; Cτ is the current adsorbent concentration, mmol; and Ce is the equilibrium adsorbent concentration, mmol.
Processing of the obtained kinetic curves shows that the pseudo-second-order model with a high value of the correlation coefficient (Table 4) describes the vanadium adsorption process. This allows us to conclude that the intensity of the sorption process depends on the concentration of active centers on the adsorbent surface, which is directly related to the number of grafted groups.
As the concentration of vanadium increases, its recovery increases. Increasing the concentration of elements contributes to the interaction with the active centers on the surface of silica. Thus, the surface is covered with metal ions. However, at high concentrations, there is competition for adsorption sites, so the rate of the process decreases.
In vanadium sorption by sorbent IV, a gradual saturation of the sorbent surface occurs. The further intensification of adsorption with increasing concentrations of the absorbed substance is explained by intraporal diffusion and the formation of a polymolecular layer.
The isotherms were treated according to the Langmuir and Freundlich equations (Table 5). The vanadium isotherm more closely corresponds to the Langmuir equation. This indicates the formation of monomolecular layers and the energy homogeneity of the modified sorbent surface. Thus, the difference in the extraction of ions can be explained by different sorption mechanisms, which are caused by the various structures of ions in the form of vanadium that exist in solutions.

3.3. Comparison with Other Sorbents

Sorption capacity is an important parameter of sorption. A comparison of this parameter for vanadium from this work with other sorbents is given in Table 6. The results presented in Table 6 show that sorbents modified with dimethylhydrazides and hydrazides are useful sorbents for the extraction of vanadium from solutions.

4. Conclusions

The chemical modification of silicon dioxide’s surface by hydrazide and dimethylhydrazide groups of Versatic acids activates its surface concerning V(V) ions. Increasing the concentration of impregnated groups on the modified sorbent promotes a greater extraction of V(V) ions. The sorption process proceeds in the intradiffusion regime, and is described by a pseudo-second-order model. It is determined not only by the concentration of vanadium ions, but also by the number of adsorption centers on the sorbent’s surface. The adsorption isotherm of V(V) ions is best described using the Langmuir model, which indicates the homogeneity of the modified sorbent surface.

Author Contributions

Conceptualization, A.G.K., E.A.B., O.A.T. and T.D.B.; methodology, A.G.K., E.A.B., O.A.T. and T.D.B.; software, A.G.K., E.A.B., O.A.T. and T.D.B.; validation, A.G.K., E.A.B., O.A.T. and T.D.B.; formal analysis, A.G.K., E.A.B., O.A.T. and T.D.B.; investigation, A.G.K., E.A.B., O.A.T. and T.D.B.; resources, A.G.K., E.A.B., O.A.T. and T.D.B.; data curation, A.G.K., E.A.B., O.A.T. and T.D.B.; writing—original draft preparation, O.A.T. and T.D.B.; writing—review and editing, O.A.T. and T.D.B.; visualization, O.A.T. and T.D.B.; supervision, A.G.K., E.A.B., O.A.T. and T.D.B. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financed under the State Contractual Order on the theme No 124020500033-8. The work was carried out using the equipment of The Core Facilities Centre “Research of Materials and Matter” at the PFRC UB RAS, and by the Ministry of Science and Higher Education Russian Federation, scientific topic No. FMEZ-2022-0018.

Data Availability Statement

All data are available in this paper.

Conflicts of Interest

The authors declare no conflicts of interest.

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Water 16 03628 g001
Figure 1. The pore distribution of the samples as a function of the specific surface value of SiO2.
Figure 1. The pore distribution of the samples as a function of the specific surface value of SiO2.
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Water 16 03628 g002
Figure 2. Structure of sorbents before (a) and after (b) surface modification with N′,N′-dimethylhydrazides.
Figure 2. Structure of sorbents before (a) and after (b) surface modification with N′,N′-dimethylhydrazides.
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Water 16 03628 g003
Figure 3. Low-temperature adsorption isotherms of nitrogen for the original (1) and modified (2) sorbents.
Figure 3. Low-temperature adsorption isotherms of nitrogen for the original (1) and modified (2) sorbents.
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Water 16 03628 g004
Figure 4. Integral (black line) and differential (blue line) curves of the pore size distribution for the original (a) and the modified sorbent (b) I+DMHD (IV).
Figure 4. Integral (black line) and differential (blue line) curves of the pore size distribution for the original (a) and the modified sorbent (b) I+DMHD (IV).
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Water 16 03628 g005
Figure 5. Sorption capacity of sorbents to ions V(V) in relation to pH (mSiO2 = 0.02 g, C(V) = 0.001 mol/L, τ = 20 min).
Figure 5. Sorption capacity of sorbents to ions V(V) in relation to pH (mSiO2 = 0.02 g, C(V) = 0.001 mol/L, τ = 20 min).
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Water 16 03628 g006
Figure 6. The dependence of the kinetic curve of adsorption of V(V) by sorbent IV at 20 °C on time (a), and the time dependence of the degree of completion of the adsorption process of V(V) by sorbent IV at 20 °C (b).
Figure 6. The dependence of the kinetic curve of adsorption of V(V) by sorbent IV at 20 °C on time (a), and the time dependence of the degree of completion of the adsorption process of V(V) by sorbent IV at 20 °C (b).
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Figure 7. Dependencies −ln(1 − F) on time t (a) and F on t1/2 (b) in the sorption of V(V) ions on sorbent IV.
Figure 7. Dependencies −ln(1 − F) on time t (a) and F on t1/2 (b) in the sorption of V(V) ions on sorbent IV.
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Figure 8. Kinetic curves of vanadium sorption: (a) pseudo-first-order and (b) pseudo-second-order.
Figure 8. Kinetic curves of vanadium sorption: (a) pseudo-first-order and (b) pseudo-second-order.
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Table 1. Sorbent production conditions and their textural parameters.
Table 1. Sorbent production conditions and their textural parameters.
Sample SiO2CSiO2, g/LCH2SO4, %pHSBET, m2/gdpor., nmvpor., cm3/g
180177136.82.300.22
280177249.82.990.40
380172693.75.730.55
4---645.82.410.33
Table 2. FTIR results of modified silica sorbents.
Table 2. FTIR results of modified silica sorbents.
Structural
Fragments 		OH,
H2O		NHC=OC-NC=NC-OHas
Si-O-Si		Has
O-Si-O		Hs
Si-O-Si
Sample
SiO24000–3000-1636---1236–1091969802
DMHD-325216581523-----
HD-329516991521-----
SiO2-DMHD3700–3000342716531533146913811239–1157–1080968805
SiO2-HD3700–3000342716601533146913811239–1157–1080968805
Table 3. Physicochemical and textural characteristics of sorbents.
Table 3. Physicochemical and textural characteristics of sorbents.
№Sorbents and Modification ConditionsSiO2:DMHDSBET, m2/gVpor, cm3/gdpor, nmpHIEPSECH+, mmol/gpKa1
ISiO2-I-693.70.555.738.341.076.60
III+DMHD 1019,
t = 25 °C		1:0.12.692.8 × 10−34.357.350.804.38
IIII+HD 1019,
t = 25 °C		1:0.10.061.8 × 10−4-7.220.954.68
IVI+DMHD 1019,
t = 25 °C		1:0.0160.800.3515.298.731.155.78
VI+DMHD 1019,
t = 80 °C		1:0.0171.560.4417.398.581.155.98
Notes: IEP—isoelectric point, SEC—static exchange capacity.
Table 4. Processing of kinetic curves of ion sorption V(V) by pseudo-first-order and pseudo-second-order equations (mSiO2 = 0.02 g, CM in the sample = 0.001 mol/L).
Table 4. Processing of kinetic curves of ion sorption V(V) by pseudo-first-order and pseudo-second-order equations (mSiO2 = 0.02 g, CM in the sample = 0.001 mol/L).
MetalR2
Pseudo-First-OrderPseudo-Second-Order
V0.3500.999
Table 5. Linearization of adsorption isotherms in the coordinates of the Langmuir and Freundlich equations.
Table 5. Linearization of adsorption isotherms in the coordinates of the Langmuir and Freundlich equations.
Equation of DependenceR2Emax, mmol/gK
V(V)/sorbent IV
Langmuiry = 4.56x + 13820.99710.72303
Freundlichy = 0.31x − 6.180.9231n3.220.002
Table 6. Sorption characteristics for vanadium sorption by various sorbents.
Table 6. Sorption characteristics for vanadium sorption by various sorbents.
SorbentSorption CapacityTimeReference
SiO20.083 mg/g240 min[3]
Coconut shell5.86 mg/g15 min[17]
HZrO@D201141.3 mg/g24 h[25]
3-APTES3.02 mmol/g30 min[27]
Bisphosphonate nanocellulose1.98 mmol/g24 h[29]
CFH-128.5 mg/g10–30 min[31]
GEH 10121.6mg/g
GWTR-Peat7.2 mg/g
Metal (hydr)oxide45.66/111.1 mg/g6 h[45]
Chitosan-Zr(IV) composite208 mg/g4 h[46]
Fe(III)/Cr(III) hydroxide waste11.43 mg/g20–80 min[47]
SiO20.19 mmol/g1 hPresent work
SiO2-DMHD4.54 mmol/g10 min
SiO2-HD3.21 mmol/g10 min
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Timoshchik, O.A.; Batueva, T.D.; Belogurova, E.A.; Kasikov, A.G. Adsorption of Vanadium (V) on Amorphous and Modified Silica. Water 2024, 16, 3628. https://doi.org/10.3390/w16243628

AMA Style

Timoshchik OA, Batueva TD, Belogurova EA, Kasikov AG. Adsorption of Vanadium (V) on Amorphous and Modified Silica. Water. 2024; 16(24):3628. https://doi.org/10.3390/w16243628

Chicago/Turabian Style

Timoshchik, Olga A., Tatiana D. Batueva, Elena A. Belogurova, and Alexander G. Kasikov. 2024. "Adsorption of Vanadium (V) on Amorphous and Modified Silica" Water 16, no. 24: 3628. https://doi.org/10.3390/w16243628

APA Style

Timoshchik, O. A., Batueva, T. D., Belogurova, E. A., & Kasikov, A. G. (2024). Adsorption of Vanadium (V) on Amorphous and Modified Silica. Water, 16(24), 3628. https://doi.org/10.3390/w16243628

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