Water pollution by pharmaceuticals is a current worrying environmental problem. Adsorption and catalytic processes using zeolites have been employed in several studies to remove/degrade pharmaceuticals from water. The interest of researchers in these two strategies based on the utilization of zeolites (i.e., adsorption and advanced oxidation technologies, AOT) is continuously growing. Then, this work presents a literature review, considering the origin of the zeolites (natural vs. synthetic) and the modifications of zeolites (e.g., the addition of surfactants) for the adsorption of diverse pharmaceuticals. The role of zeolites in catalytic ozonation, Fenton-based systems, and activation of peroxymonosulfate and peroxydisulfate is detailed. Also, the primary transformations of pharmaceuticals induced by these AOTs were examined. Moreover, the gaps regarding biodegradability and toxicity of the transformation products coming from the degradation of pharmaceuticals by the zeolites-based processes were discussed. To overcome the scarcity of information regarding the biodegradability and toxicity of the primary transformation products observed in the revised works, an initial approach to these topics, using a predictive tool, was made. Finally, from the present review, it was evidenced the need for future works involving zeolites that provide results about the simultaneous removal/elimination of multiple pharmaceuticals in complex matrices (e.g., hospital wastewater or municipal wastewater), new information about biodegradability and toxicity plus the development of combination or coupling of processes with other AOTs (e.g., sonochemistry) or classical systems (e.g., biological process).
24 February 2024 in International Journal of Hydrogen Energy
Mid-high-frequency ultrasound (200–1000 kHz) eliminates organic pollutants and also generates H2O2. To take advantage of H2O2, iron species can be added, generating a hybrid sono-Fenton process (sF). This paper presents the possibilities and limitations of sF. Heterogeneous (a natural mineral) and homogeneous (Fe2+ and Fe3+ ions) iron sources were considered. Acetaminophen, ciprofloxacin, and methyl orange were the target organic pollutants. Ultrasound alone induced the pollutants degradation, and the dual competing role of the natural mineral (0.02–0.20 g L−1) meant that it had no significant effects on the elimination of pollutants. In contrast, both Fe2+ and Fe3+ ions enhanced the pollutants’ degradation, and the elimination using Fe2+ was better because of its higher reactivity toward H2O2. However, the enhancement decreased at high Fe2+ concentrations (e.g., 5 mg L−1) because of scavenger effects. The Fe2+ addition significantly accelerated the elimination of acetaminophen and methyl orange. For ciprofloxacin, at short treatment times, the degradation was enhanced, but the pollutant complexation with Fe3+ that came from the Fenton reaction caused degradation to stop. Additionally, sF did not decrease the antimicrobial activity associated with ciprofloxacin, whereas ultrasound alone did. Therefore, the chemical structure of the pollutant plays a crucial role in the feasibility of the sF process.
A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L−1), limiting its use for water treatment. To avoid leaching, Φy was calcinated, forming a mixed metal oxide (MMO). In the combination of MMO/PMS, no metals leached, the CIP adsorption was low (95% after 15 min of treatment). MMO/PMS promoted the opening and oxidation of the piperazyl ring, plus the hydroxylation of the quinolone moiety on CIP, which potentially decreased the biological activity. After three reuse cycles, the MMO still presented with a high activation of PMS toward CIP degradation (90% in 15 min of action). Additionally, the CIP degradation by the MMO/PMS system in simulated hospital wastewater was close to that obtained in distilled water. This work provides relevant information on the stability of Co-, Cu-, and Cr-based materials under interaction with PMS and the strategies to obtain a proper catalyst to degrade CIP.
A new trimetallic compound with formula (NH 4 )H 2 Co 2 O(OH)(MoO 4 ) 1.6 (WO 4 ) 0.4 •H 2 O and lamellar structure was prepared by hydrothermal synthesis. The solid was characterized using X-ray diffraction (XRD), thermogravimetric (TGA) and differential thermal (DTA) analyses, Fourier-transform infrared spectroscopy (FT–IR), laser Raman spectroscopy (LRS), and atomic absorption spectroscopy (AA). Crystallographic studies showed that the solid crystallizes with hexagonal symmetry in space group R -3 m with a = 6.0807 and c = 21.7591 Å.
In the field of hydrocracking reactions, achieving optimal middle distillate yields remains a persistent challenge with commercially available zeolite Y catalysts. This limitation is attributed to challenges related to diffusion constraints within the catalyst. In response, we present a promising solution not only to these problems but also to the challenges encountered in nanosized Y zeolites when attempting to generate acidic sites within their structure and when analyzing their performance in vacuum gas oil hydrocracking. NiMo catalysts based on nanosized Y zeolites with different crystal sizes exchanged with lanthanum, effectively address diffusion issues and significantly enhance catalyst performance compared to dealuminated nanosized and commercial Y zeolite under the same reaction conditions. The catalysts were characterized by TGA, ICP-OES, XPS, N2 physisorption, FT-IR for pyridine acidity, TEM-mapping, and the 3-methyl thiophene reaction to test the hydrogenating capacity. Surface analysis and microscopy showed greater porosity in the catalysts with smaller zeolites and different arrangements of their components. The catalysts based on steamed protonated nanosized Y zeolites with a larger size and lanthanide nanosized Y zeolite with a smaller size yielded more middle distillates. Research provides a comprehensive analysis, providing a correlation between the catalytic performance and the size of the nanosized Y zeolite.