Elsevier

Water Research

Volume 185, 15 October 2020, 116212
Water Research

Removal of p-aminobenzenesulfanilamide from water solutions by catalytic photo-oxidation over Fe-pillared clay

https://doi.org/10.1016/j.watres.2020.116212Get rights and content

Highlights

  • Fe-pillared clay was active catalyst for aminobenzenesulfanilamide photo-oxidation.

  • Influence of physicochemical parameters on the photo-oxidation kinetics were studied.

  • The photo-oxidative degradation intermediate products were determined by HPLC.

  • The catalyst was stable in three consecutive cycles without regeneration.

Abstract

The catalytic photo-oxidation of p-aminobenzenesulfanilnamide (ABS) with hydrogen peroxide in the presence of Fe-pillared clay as heterogeneous catalyst has been investigated under UV-irradiation (λmax = 254 nm). Fe-pillared clay was synthesized by intercalating the iron polyhydroxycomplexes into the interlayer space of a natural layered aluminosilicate - montmorillonite and a subsequent heat treatment at 500 °C. The catalyst was characterized by chemical analysis, low temperature nitrogen adsorption and XRD. The kinetics of photocatalytic oxidative degradation of ABS in aqueous solutions under various experimental conditions was studied. The dependence of the photo-oxidation rate on such experimental factors as pH, hydrogen peroxide concentration and catalyst content was established. The conversion of ABS was 100% and the mineralization efficiency was 52.3% at optimal conditions. The intermediate products of ABS photo-oxidation identified by HPLC were a sulfanilic acid, benzenesulfonamide, benzenesulfonic acid, hydroquinone, pyrocatechol, benzoquinone and aliphatic acids. Fe-pillared clay remained highly active in three consecutive catalytic cycles without regeneration. The results of the study suggested that the heterogeneous photo-system «Fe-pillared clay/H2O2/UV» was effective in the oxidative degradation of aminobenzenesulfanilnamide. This system may be of interest for use in organic wastewater treatment processes.

Introduction

Currently, the environmental pollution with toxic industrial and household waste of human activity, among which the experts include pharmaceutical compounds, referring to them as “drug pollution” has become the global environmental problem. The growing volumes of production and use of pharmaceuticals lead to their uncontrolled release into the environment, while many of them are poorly biodegradable (Kümmerer, 2009; Chen and Xie, 2018). Residual pharmaceutical substances were found in groundwater and surface water, drinking and tap water, as well as in bottom sediments and soil. Drug pollution is particularly dangerous because they exhibit high biological activity in trace amounts, which adversely affects humans and animals (Snyder et al., 2010; Baran et al., 2011; Li, 2014; Owens, 2015; Sharma et al., 2019). Sulfanilamides (SA) belong to an important group of drugs which are widely used to treat many infectious diseases. p-Aminobenzenesulfamide is the structural basis for the synthesis of numerous sulfonamides drugs (Hommem and Santos, 2011; Magureanu et al., 2015; Wang and Wang, 2016).

The main sources of environmental pollution by sulfonamides are pharmaceutical plants, medical and veterinary institutions, livestock and poultry farms, as well as agricultural enterprises where sulfonamide compounds are used as herbicides. SA can also be contained in the wastewater of chemical plants, where they are used to produce synthetic dyes. The high polarity and non-volatility of most sulfanilamide compounds facilitate their migration and release into groundwater and soil (Hommem and Santos, 2011; Brown and Wong, 2018; Miller et al., 2018). The biochemical decomposition of these compounds is hindered by their toxicity to microorganisms, while their prolonged exposure increases the resistance of pathogenic bacteria to drugs, which poses a threat to human health. To prevent the penetration of pharmaceutical compounds into natural water bodies and soils, it is necessary to treat wastewater using various physicochemical methods such as adsorption on natural and synthetic materials (Braschi et al., 2010; Ji et al., 2013; Liu et al., 2015; Sayğılı et al., 2016; Ahmed et al., 2017; Peng et al., 2019), membrane filtration (Ganiyu et al., 2015; Rosman et al., 2018; Zhao et al., 2018), chlorination (Adams et al., 2002), electrooxidation (Ferraz et al., 2018), advanced oxidation (Boreen et al., 2004; Xekoukoulotakis et al., 2011; Rivera-Utrilla et al., 2013; Mirzaei et al., 2016; Tačić et al., 2017; Hinojosa Guerra et al., 2019), as well as filtration through active media (porous polymers, hydrogels) (Alsbaiee et al., 2015; Ji et al., 2018; Xu et al., 2019) and biodegradation by various microorganisms (Pan et al., 2018; Wang et al., 2018). Advanced oxidation processes (AOP) are the most effective of the modern methods of wastewater treatment from organic pollutants. These processes are based on the “in situ” generation of free radicals (HO, O2−∙, HO2), the most highly active of which are hydroxyl radicals capable of rapidly oxidizing numerous organic compounds (Timofeeva et al., 2005; Pignatello et al., 2006; Iurascu et al., 2009; Cheng et al., 2016; Kanakaraju et al., 2018; Miklos et al., 2018; Khankhasaeva, 2019). Such processes include catalytic oxidation in aqueous phase using as oxidizer air (CWAO), ozone or hydrogen peroxide (CWPO) (Klavarioti et al., 2009; Wang et al., 2019). The use of catalysts significantly reduces the temperature and pressure at which the oxidation processes of organic compounds occur and allow to achieve a high degree of their degradation up to complete mineralization with the formation of carbon dioxide, water and inorganic ions. The widespread use of hydrogen peroxide in wastewater treatment is due to its technological advantages compared to other oxidizing agents (high solubility in water, stability, the ability to treat water in a wide temperature range, the simplicity of the equipment used) (Tijani et al., 2014). The most famous oxidizing systems are Fenton and photo-Fenton systems (Fe2+/H2O2, Fe2+/H2O2, hν), a high activity of which is due to the generation of hydroxyl radicals upon activation of hydrogen peroxide by iron ions (Pignatello et al., 2006; Navalon et al., 2010; Herney-Ramirez et al., 2010; Pouran et al., 2015; Mirzaei et al., 2017):Fe2++H2O2Fe3++OH+HO·Fe3++H2O2Fe2++HOO·+H+HO·+RR1where R is an organic compound, R1 is the product of its oxidation.

Hydroxyl radicals having a high oxidation potential (Eo = 2.80 V) quickly and non-selectively oxidize numerous organic compounds. The important advantages of photo-Fenton processes include the additional reactions for the generation of hydroxyl radicals and the decrease in the amount of formed iron sludge in comparison with traditional Fenton system (Pignatello et al., 2006). The high efficiency of photo-Fenton systems is caused by an increase in the rate of hydroxyl radicals formation due to the photoreduction of Fe3+ cations and H2O2 photolysis, which represent an additional source of hydroxyl radicals (Neyens and Baeyens, 2003; Zhang et al., 2019):Fe3++H2OhvFe2++HO·+H+H2O2hv2HO·

Homogeneous Fenton and photo-Fenton systems were used to effective remove toxic organic compounds contained in wastewaters of various industries (phenol, azo dyes, pesticides, alcohols, organic acids, etc.) and were widely described in the literature (Centi and Perathoner, 2008; Garrido-Ramírez et al., 2010; Santos et al., 2011; Khankhasaeva et al., 2013, 2017; Liu et al., 2013; Clarizia et al., 2017). The significant disadvantages of homogeneous Fenton systems are their high activity within a narrow range of strongly acidic pH values, the use of solutions with high iron concentrations and the difficulty in separating dissolved iron salts from the liquid reaction mass after the oxidation reaction. A neutralization step is required to remove the dissolved catalyst from water. This causes an additional consumption of reagents, and the formation of a large amount of precipitated iron hydroxides, which are discharged into the environment. It is necessary to convert iron hydroxides to soluble salts by acidification for regeneration and reuse of the catalyst, which greatly increases the cost of water treatment processes.

These problems can be avoided by use of Fenton-type heterogeneous systems in which the catalysts are iron cations immobilized on solid matrices (Khankhasaeva et al., 2008; Navalon et al., 2010; Herney-Ramirez et al., 2010; Pouran et al., 2015; Baloyi et al., 2018). Among the heterogeneous catalysts for oxidation processes, pillared clays (PILCs) are currently of great interest. Pillared materials are obtained by exchanging cations of alkali and alkaline-earth metals located in the interlayer space of layered aluminosilicates for bulky polyoxocations of iron or other polyvalent metals and their subsequent heat treatment, leading to the formation of metal oxide clusters between aluminosilicate layers (Timofeeva and Khankhasaeva, 2009; Gil et al., 2011; Vicente et al., 2013). As a result of these processes, microporous materials with a layered columnar structure are formed in which metal oxide particles play a structure-forming role and at the same time they are the catalytic centers for chemical reactions. Recent studies have shown that Fe- and Cu-pillared clays exhibit a high catalytic activity in the processes of Fenton and photo-Fenton oxidation of phenols and other toxic organic pollutants (Carriazo et al., 2005; Luo et al., 2009; Timofeeva et al., 2009a; Timoveeva et al., 2009b; Bel et al., 2015; Guimaraes et al., 2019). Along with a high activity pillared clays have high specific surface and stability to leaching of active metals into aqueous phase, which makes it possible to use them repeatedly without regeneration in Fenton oxidation reactions and also they are characterized by the simplicity of their synthesis method, low cost and availability of initial clay raw materials and environmental safety. For example, it was shown (Bel et al., 2015) that Cu-doped Fe-pillared clay Cu/Fe-PILC exhibited a high catalytic activity in the heterogeneous photo-Fenton oxidation of phenol in an aqueous solution irradiated with UV light: phenol conversion was 100% after 40 min at pH 5.05 and the mineralization of phenol was 99% after 70 min. A slight leaching of active metals and reuse of the catalyst in three cycles without a noticeable loss of activity (about 2%) confirmed the excellent catalytic stability of the Cu/Fe-PILC catalyst. A successful use of Al-Cu- and Al-Fe-pillared clays (Al-Cu-ST and Al-Fe-ST) as heterogeneous photocatalysts for the purification of real wine-making wastewater, which were characterized by a high content of stable polyphenolic compounds was described in (Guimaraes et al., 2019). The Al-Cu-ST showed a higher activity than Al-Fe-ST, but also it showed a lower stability in three consecutive cycles at pH 3.0. The TOC removal was 79.3, 75.5 and 75.2% (Al-Cu-ST) and 67.1, 61.6 and 57.9% (Al-Fe-ST) from the 1st to the 3rd cycle. The concentrations of leached metal ions were below the maximum permissible concentrations ([Cu] <1 mg/l, [Fe] <2 mg/l) in both cases. The photo-Fenton oxidation of 4-chlorophenol catalyzed by Al-Fe PILC and irradiated with UV-A light was described in (Catrinescu et al., 2012). The complete decomposition of 4-chlorophenol occurred in 120 min under the following conditions: [H2O2]/[4-chlorophenol] = 13.5: 1 (molar ratio), pH 3.5, [Al-Fe PILC] 0.5 g/l, 30 °C. The obtained experimental data allowed the authors to suggest that photo-Fenton oxidation of 4-chlorophenol catalyzed by Al-Fe PILC proceeded according to a heterogeneous-homogeneous mechanism. Fe-PILC samples with different iron contents (6.1, 13.4, and 17.6%) were obtained by introducing the tri-nuclear complex Fe (III) acetate and further calcining at 400°С (De Leon et al., 2017). Fe-PILCs were active as catalysts for photo-Fenton decomposition of phenol using UVA radiation. The maximum oxidation rate was observed for Fe-PILC containing 13.4% of iron. The leaching of iron from the obtained catalysts did not exceed 1.3 mg/l and the mineralization of phenol solution was 61%. The liquid phase catalytic degradation of sulfanilamide with H2O2 was carried out in acidic medium in the presence of two-component Fe/Al-pillared clay as heterogeneous Fenton type catalyst (Khankhasaeva et al., 2015). It was found that the pH of reaction medium, H2O2 concentration and the reaction temperature affected the induction period, which could be explained by the radical generation from H2O2 on the surface of the catalyst. The increasing acidity of the reaction mixture from pH 4.1 to 3.1 favored the rising of sulfanilamide conversion from 14 to 39% after 60 min of reaction. The conversion of sulfanilamide was 95–99% for 360 min at pH 3.1 and 4.1. Leaching of Fe species from Fe/Al- pillared clay and their effect on the reaction rate were negligible. The increasing reaction temperature and H2O2/sulfanilamide molar ratio increased the reaction rate. The Fe/Al-clay catalyst could be used repeatedly without significant loss of catalytic activity during at least three catalytic cycles. Fe/Cu/Al-pillared clays were proved to be the promising catalysts for oxidative degradation of sulfanilamide with hydrogen peroxide in aqueous solutions: in the presence of these materials oxidation rate increased significantly and the conversion of sulfanilamide reached 99–100% (Khankhasaeva et al., 2017). Three-component systems Fe/Cu/Al-pillared clays had a greater activity than two-component systems Fe/Al- pillared clay and Cu/Al-pillared clay, that due to the combined catalytic effect of iron and copper ions. The optimal conditions for the catalytic oxidation of sulfanilamide in the presence of Fe/Cu/Al-pillared clay, allowing to achieve a high conversion of sulfanilamide and catalyst stability were determined: 2 g/dm3 of catalyst, pH =3.5–4.0, molar ratio [H2O2]/[sulfanilamide] = 18, 30–50°С. Fe/Cu/Al- pillared clay could be used in four consecutive cycles without regeneration and loss of activity.

The present study provides the results describing the heterogeneous photocatalytic oxidation of p-aminobenzenesulfanilamide (ABS) over Fe-pillared montmorillonite clay under various experimental conditions.

Section snippets

Materials

The starting material for producing Fe-pillared clay was bentonite clay of Mukhortala deposit (Russia, Buryatia) with 90% of montmorillonite. The chemical composition of the fine fraction (particle size <0.001 mm) introduced oxides (wt%): SiO2 - 65.50; Al2O3 −14.50; Na2O - 0.16; K2O - 0.17; MgO - 1.36; CaO - 1.06; ZnO - 0.018; MnO - 0.002; Fe2O3 - 1.07; CuO - 0.002; H2O - 16.16. p-Aminobenzenesulfanilamide (C6H8N2O2S) was purchased from Lyumi Company (Russia). FeCl3 • 6H2O, NaOH, H2SO4 were

Catalyst characterization

The diffraction patterns of natural clay dried at room temperature and calcined at 500 °C were shown in Fig. 1.

Diffractions that corresponded to montmorillonite and the impurity mineral cristobalite were identified on the diffractogram of an oriented sample of natural clay (Moore and Reynolds, 1997). The first basal diffraction shifted to small angles 2θ upon saturation of the sample with ethylene glycol (Fig. 1a) and the basal spacing d001 increased from 1.42 nm to 1.77 nm, which was due to

Conclusion

Fe-pillared clay was synthesized from natural layered aluminosilicate - montmorillonite by intercalating iron polyhydroxycomplexes into its interlayer space and the subsequent heat treatment at 500 °C and characterized by chemical analysis, low temperature nitrogen adsorption and XRD. The iron content in Fe-pillared clay was 50.3 mg/g, specific surface area was 130 m2/g. It was shown that Fe-pillared clay was active catalyst for the photo-oxidation of p-aminobenzenesulfanilamide with hydrogen

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was carried out with support from the Program of Basic Research of Baikal Institute of Nature Management SB RAS.

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