Removal of Phenolic Compounds from Water Using Copper Ferrite Nanosphere Composites as Fenton Catalysts

The authors affiliated to the University of Jaén (Department of Inorganic and Organic Chemistry) acknowledge financial support from the Spanish Ministry of Economy, Industry and Competitiveness and from FEDER (Project CTQ2016-80978-C2-1-R). L. Mateus thanks the Asociación Universitaria Iberoamericana de Postgrado (AUIP) and University of Jaén for their grant and financial support.Copper ferrites containing Cu+ ions can be highly active heterogeneous Fenton catalysts due to synergic effects between Fe and Cu ions. Therefore, a method of copper ferrite nanosphere (CFNS) synthesis was selected that also permits the formation of cuprite, obtaining a CFNS composite that was subsequently calcined up to 400 °C. Composites were tested as Fenton catalysts in the mineralization of phenol (PHE), p-nitrophenol (PNP) and p-aminophenol (PAP). Catalysts were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. Degradation of all phenols was practically complete at 95% total organic carbon (TOC) removal. Catalytic activity increased in the order PHE < PNP < PAP and decreased when the calcination temperature was raised; this order depended on the electronic effects of the substituents of phenols. The as-prepared CFNS showed the highest catalytic activity due to the presence of cubic copper ferrite and cuprite. The Cu+ surface concentration decreased after calcination at 200 °C, diminishing the catalytic activity. Cuprite alone showed a lower activity than the CFNS composite and the homogeneous Fenton reaction had almost no influence on its overall activity. CFNS activity decreased with its reutilization due to the disappearance of the cuprite phase. Degradation pathways are proposed for the phenols.This research was funded by Spanish Ministry of Economy, Industry and Competitiveness and FEDER (grant number CTQ2016-80978-C2-1-R), Asociación Universitaria Iberoamericana de Postgrado (AUIP) and University of Jaén

Kinetics of diuron and amitrole adsorption from aqueous solution on activated carbons

A study was conducted on the adsorption kinetics of diuron and amitrole from aqueous solutions on activated carbons of different particle sizes and on an activated carbon fiber. Different kinetic models were applied to the experimental results obtained. A pseudo-second-order rate equation fitted the adsorption kinetics data better than a pseudo-first-order rate equation. Amitrole showed faster adsorption kinetics compared with diuron because of the smaller size of the former herbicide, despite its lower driving force for adsorption. Both reaction rate constants increased when the particle size decreased. The activated carbon fiber and the activated carbon of smallest particle size (0.03 mm) showed similar adsorption kinetics. The intraparticle diffusion rate constant increased with higher initial concentration of herbicides in solution and with lower particle size of the adsorbent. This is because the rise in initial concentration increased the amount adsorbed at equilibrium, and the reduction in particle size increased the number of collisions between adsorbate and adsorbent particles. Demineralization of the activated carbon with particle size of 0.5 mm had practically no effect on the adsorption kinetics

Batch and column adsorption of herbicide fluroxypyr on different types of activated carbons from water with varying hardness and alkalinity degrees

There has been little research into the effects of the water hardness and alkalinity of surface waters on the adsorption of herbicides on activated carbons. The aim of this study was to determine the influence of these water characteristics on fluroxypyr adsorption on different activated carbons. At low fluroxypyr surface concentrations, the amount adsorbed from distilled water was related to the surface hydrophobicity. Surface area of carbons covered by fluroxypyr molecules ranged from 60 to 65%. Variations in fluroxypyr solubility with water hardness and alkalinity showed a salting-in effect. Calcium, magnesium and bicarbonate ions were adsorbed to a varied extent on the activated carbons. The presence of fluroxypyr in solution decreased their adsorption due to a competition effect. KF from the Freundlich equation linearly increased with water hardness due to salt-screened electrostatic repulsions between charged fluroxypyr molecules. The amount adsorbed from distilled water was largest at high fluroxypyr solution concentrations, because there was no competition between inorganic ions and fluroxypyr molecules. The column breakthrough volume and the amount adsorbed at breakthrough were smaller in tap versus distilled water. Carbon consumption was lower with activated carbon cloth than with the use of granular activated carbon.The authors are grateful to MEC and FEDER project CTQ2007-67792-C02-02 and Junta de Andalucía project RNM 547 for financial support. LMPM acknowledges receipt of an MEC pre-doctoral fellowship

Extraction and Depolymerization of Lignin from Different Agricultural and Forestry Wastes to Obtain Building Blocks in a Circular Economy Framework

Large amounts of agri-food waste are generated and discarded annually, but they have the potential to become highly profitable sources of value-added compounds. Many of these are lignin-rich residues. Lignin, one of the most abundant biopolymers in nature, offers numerous possibilities as a raw material or renewable resource for the production of chemical products. This study aims to explore the potential revalorization of agricultural by-products through the extraction of lignin and subsequent depolymerization. Different residues were studied; river cane, rice husks, broccoli stems, wheat straw, and olive stone are investigated (all local wastes that are typically incinerated). Traditional soda extraction, enhanced by ultrasound, is applied, comparing two different sonication methods. The extraction yields from different residues were as follows: river cane (28.21%), rice husks (24.27%), broccoli (6.48%), wheat straw (17.66%), and olive stones (24.29%). Once lignin is extracted, depolymerization is performed by three different methods: high-pressure reactor, ultrasound-assisted solvent depolymerization, and microwave solvolysis. As a result, a new microwave depolymerization method has been developed and patented, using for the first time graphene nanoplatelets (GNPs) as new promising carbonaceous catalyst, achieving a 90.89% depolymerization rate of river cane lignin and yielding several building blocks, including guaiacol, vanillin, ferulic acid, or acetovanillone

Competitive adsorption of the herbicide fluroxypyr and tannic acid from water on activated carbons and their thermal desorption

A study was conducted on batch and column competitive adsorption of fluroxypyr (FLX) and tannic acid (TA) from distilled (DW) and tap water (TW) on activated carbon cloth (ACC) and granular activated carbon (GAC). Thermal desorption of the adsorbates from the spent ACC was also studied. FLX adsorption was higher from TW than from DW at low FLX equilibrium concentrations, and the inverse was observed at high FLX concentrations. The pres- ence of TA diminished the amount of FLX adsorbed from both solvents due to partial blocking of the microporosity, but the same trends as before were observed at low and high FLX concentrations. Carbon consumption, obtained from the breakthrough curves, was lower as a function of superfi- cial contact time with ACC than with GAC. The presence of TA increased carbon consumption, which was related to the microporosity of the adsorbents. Thermal desorption pro- files of the spent ACC showed two peaks and one peak af- ter adsorption from DW and TW, respectively. Desorption peaks shifted to higher temperatures with an increase in the heating rate, allowing the apparent activation energies an pre-exponential factors of the desorption processes to be de- terminedThe authors are grateful to MICINN and FEDER, project CTQ2011-29035-C02-01, for financial suppor