Dynamics and Kinetics of Cupric Ion Removal from Wastewaters by Tunisian Solid Crude Olive-Oil Waste.
ABSTRACT: The present paper aims to develop a low cost, efficient, and environmentally-friendly process to purify (industrial) waters contaminated by copper by the use of oil mill wastes, through kinetic, thermodynamic, and equilibrium investigations. To do so, the raw adsorbent was characterized using different analytical techniques including X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Then, the interaction between copper and olive residues were examined during batch adsorption tests at various operating parameters, such as pH, initial concentration, contact time, and particle size. Kinetic data were best fitted with Broeurs-Sotolongo kinetic model. Additionally, it was found that film and intraparticle diffusion steps controlled simultaneously the mass transfer of copper onto olive mill solid waste. Among the eight tested models, Broeurs-Sotolongo isotherm suited the most the sorption, with regards to the function errors analysis. It was deduced that the adsorption of copper does not involve chemical bonds with high energy which allows easier regeneration steps and higher number of biosorbent regeneration cycles without any need for applying high temperature in the desorption reaction systems. The adsorption capacity (18.93 mg/g) calculated on the basis of this model was close to the experimental value (18.4 mg/g) but more interestingly it brought up that 50% of the generated amounts of olive wastes in Tunisia could eliminate 1.84 kTons of copper from industrial waters.
Project description:During olive oil extraction, large amounts of phenolics are generated in the corresponding wastewaters (up to 10 g dm-3). This makes olive oil mill wastewater toxic and conventional biological treatment challenging. The catalytic wet peroxide oxidation process can reduce toxicity without significant energy consumption. Hydrogen peroxide oxidation of phenolics present in industrial wastewaters was studied in this work over copper catalysts focusing on understanding the impact of mass transfer and establishing the reaction kinetics. A range of physicochemical methods were used for catalyst characterization. The optimal reaction conditions were identified as 353 K and atmospheric pressure, giving complete conversion of total phenols and over 50% conversion of total organic carbon content. Influence of mass transfer on the observed reaction rate and kinetics was investigated, and parameters of the advanced kinetic model and activation energies for hydrogen peroxide decomposition and polyphenol oxidation were estimated.
Project description:Activated carbons were prepared from a lignocellulosic material, African palm shells (Elaeis guineensis), by chemical impregnation of the precursor with solutions of 1-7% w/v Cu(NO3)2 at five different concentrations. These were carbonized in a carbon dioxide atmosphere at 1073 K to obtain different carbons. Their textural properties were characterized by nitrogen and carbon dioxide adsorption isotherms in order to evaluate the pore-size distribution. The immersion enthalpies of the activated carbons in benzene, dichloromethane, and water were determined. The CO2 adsorption capacities of the materials at 273 K under low-pressure conditions were also determined. Chemical characterization was performed by mass spectrometry, Fourier transform infrared spectroscopy, and temperature-programmed reduction. With this method of preparation under the concentrations described, activated micro-mesoporous carbons were obtained, with the formation of highly mesoporous solids that favored the process of diffusion of molecules of CO2 into the material. Here, we show that activated carbons were obtained with different textural characteristics: surface Brunauer-Emmett-Teller areas varied between 473 and 1361 m2 g-1 and micropore volume between 0.18 and 0.51 cm3 g-1. The activated carbon with the highest values of textural parameters was ACCu5-1073. Micro-mesoporous solids were obtained with the methodology used. This is important as it may help the entry of CO2 molecules into the pores. The adsorption of CO2 in the materials prepared presented values between 103 and 217 mg CO2 g-1; the values of volume of narrow microporosity obtained were between 0.16 and 0.45 cm3 g-1. The solid with the greatest capacity for adsorption of CO2 and volume of narrow microporosity was ACCu3-1073. The use of these solids is of importance for future practical and industrial applications. The adsorption kinetic of CO2 in the activated carbons prepared with metallic salt of copper is in good accordance with the intraparticle diffusion model, for which diffusion is the rate-limiting step. The adsorption of CO2 in the prepared activated carbons is favorable from the energy and kinetic point of view, as these accompanied by the presence of wide micro-mesoporosity favor the entry of CO2 into the micropores.
Project description:Over the past decade, the increasing demand of vegetable oils for biodiesel production has highlighted the need for alternative oil feedstocks that do not compete with food production. In this context, the combined use of agro-industrial wastes and oleaginous microorganisms could be a promising strategy for sustainable biodiesel production. The present investigation involves the performance of the oleaginous yeast Wickerhamomyces anomalus strain EC28 to produce lipids from different agro-industrial wastewaters (i.e., deproteinized cheese whey, olive mill wastewater, and wastewaters from confectionary industries) and waste frying oils (i.e., waste oil from frying fish, waste oil from frying potato and waste oil from frying meat). Results indicated that this strain can adequately grow on agro-industrial wastewater-based media and produce substantial amounts of lipids [up to 24%, wt/wt in deproteinized cheese whey-based medium and olive mill wastewater-based medium (75%, v/v in water)] of similar fatty acid composition to that of the most commonly used vegetable oils in the biodiesel industry. However, the addition of frying oils to the culture media resulted in a significant decrease in total lipid content, probably due to excess of available nitrogen released from meat, fish, and potato into the frying oil. The estimated properties of the resulting biodiesels, such as SV (190.69-203.13), IV (61.77-88.32), CN (53.45-59.32), and CFPP (-0.54 to 10.4), are reported, for the first time, for W. anomalus and correlate well with specified standards. In conclusion, W. anomalus strain EC28, for which there is very limited amount of available information, might be regarded as a promising candidate for biodiesel production and additional efforts for process improvement should be envisaged.
Project description:Adsorption on low-cost biochars would increase the affordability and availability of water treatment in, for example, developing countries. The aim of this study was to identify the precursor materials and hydrochar surface properties that yield efficient removal of compounds of environmental concern (CEC). We determined the adsorption kinetics of a mixture containing ten CECs (octhilinone, triclosan, trimethoprim, sulfamethoxasole, ciprofloxacin, diclofenac, paracetamol, diphenhydramine, fluconazole, and bisphenol A) to hydrochars prepared from agricultural waste (including tomato- and olive-press wastes, rice husks, and horse manure). The surface characteristics of the hydrochars were evaluated via diffuse reflectance infrared spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and N2-adsorption. Kinetic adsorption tests revealed that removal efficiencies varied substantially among different materials. Similarly, surface analysis revealed differences among the studied hydrochars and the degree of changes that the materials undergo during carbonization. According to the DRIFTS data, compared with the least efficient adsorbent materials, the most efficient hydrochars underwent more substantial changes during carbonization.
Project description:The valorization of food wastes is a challenging opportunity for a green, sustainable, and competitive development of industry. Approximately 30 million m3 of olive mill wastewater (OMWW) are produced annually in the world as a by-product of the olive oil extraction process. In addition to being a serious environmental and economic issue because of their polluting load, OMWW can also represent a precious resource of high-added-value molecules such as polyphenols that show acclaimed antioxidant and anti-inflammatory activities and can find useful applications in the pharmaceutical industry. In particular, the possibility to develop novel nutraceutical ophthalmic formulations containing free radical scavengers would represent an important therapeutic opportunity for all inflammatory diseases of the ocular surface. In this work, different adsorbents were tested to selectively recover a fraction that is rich in polyphenols from OMWW. Afterward, cytotoxicity and antioxidant/anti-inflammatory activities of polyphenolic fraction were evaluated through in vitro tests. Our results showed that the fraction (0.01%) had no toxic effects and was able to protect cells against oxidant and inflammatory stimulus, reducing reactive oxygen species and TNF-? levels. Finally, a novel stable ophthalmic hydrogel containing a polyphenolic fraction (0.01%) was formulated and the technical and economic feasibility of the process at a pre-industrial level was investigated.
Project description:A series of biochars and activated carbons (ACs) was prepared combining carbonization and physical or chemical activation of cheap and abundant residues of the olive oil industry. These materials were used as Fe-support to develop low-cost catalysts for the heterogeneous Fenton-like oxidation of simulated olive mill wastewater (OMW), the highly pollutant effluent generated by this agroindustry. Commercial ACs were also used as reference. All catalysts prepared were extensively characterized and results related with their performances in the catalytic wet peroxide oxidation (CWPO). Results showed a linear relationship of the textural properties of the catalysts with the adsorptive and catalytic performance, as well as the preferential adsorption and degradation of some phenolic compounds (caffeic and gallic acids) by specific interactions with the catalysts' surface. Despite the best performance of catalysts developed using commercial supports, those prepared from agro-industrial residues present some advantages, including a smaller catalyst deactivation by iron leaching. CWPO results show that catalysts from physically activated olive stones are the most promising materials, reaching total organic carbon and toxicity reductions of 35% and 60%, respectively, as well an efficient use of H2O2, comparable with those obtained using commercial supports. This approach showed that the optimized treatment of this type of residues will allow their integration in the circular economic process of the olive oil production.
Project description:Biosorption process is a promising technology for the removal of heavy metals from industrial wastes and effluents using low-cost and effective biosorbents. In the present study, adsorption of Pb(2+), Cu(2+), Fe(2+), and Zn(2+) onto dried biomass of red seaweed Kappaphycus sp. was investigated as a function of pH, contact time, initial metal ion concentration, and temperature. The experimental data were evaluated by four isotherm models (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) and four kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models). The adsorption process was feasible, spontaneous, and endothermic in nature. Functional groups in the biomass involved in metal adsorption process were revealed as carboxylic and sulfonic acids and sulfonate by Fourier transform infrared analysis. A total of nine error functions were applied to validate the models. We strongly suggest the analysis of error functions for validating adsorption isotherm and kinetic models using linear methods. The present work shows that the red seaweed Kappaphycus sp. can be used as a potentially low-cost biosorbent for the removal of heavy metal ions from aqueous solutions. Further study is warranted to evaluate its feasibility for the removal of heavy metals from the real environment.
Project description:Population dynamics of methanogenic genera was investigated in pilot anaerobic digesters. Cattle manure and two-phase olive mill wastes were codigested at a 3:1 ratio in two reactors operated at 37 ﾰC and 55 ﾰC. Other two reactors were run with either residue at 37 ﾰC. Sludge DNA extracted from samples taken from all four reactors on days 4, 14 and 28 of digestion was used for hybridisation with the AnaeroChip, an oligonucleotide microarray targeting those groups of methanogenic archaea that are commonly found under mesophilic and thermophilic conditions (Franke-Whittle et al. 2009, in press, doi:10.1016/j.mimet.2009.09.017).
Project description:Dietary phytochemicals are particularly attractive for chemoprevention and are able to modulate several signal transduction pathways linked with cancer. Olive oil, a major component of the Mediterranean diet, is an abundant source of phenolic compounds. Olive oil production is associated with the generation of a waste material, termed 'olive mill wastewater' (OMWW) that have been reported to contain water-soluble polyphenols. Prostate cancer (PCa) is considered as an ideal cancer type for chemopreventive approaches, due to its wide incidence but relatively long latency period and progression time. Here, we investigated activities associated with potential preventive properties of a polyphenol-rich olive mill wastewater extract, OMWW (A009), on three in vitro models of PCa. A009 was able to inhibit PCa cell proliferation, adhesion, migration, and invasion. Molecularly, we found that A009 targeted NF-?B and reduced pro-angiogenic growth factor, VEGF, CXCL8, and CXCL12 production. IL-6/STAT3 axis was also regulated by the extract. A009 shows promising properties, and purified hydroxytyrosol (HyT), the major polyphenol component of A009, was also active but not always as effective as A009. Finally, our results support the idea of repositioning a food waste-derived material for nutraceutical employment, with environmental and industrial cost management benefits.
Project description:The new cupric superoxo complex [LCu(II)(O(2)(•-))](+), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases.