Carbonaceous materials from a petrol primary oily sludge: Synthesis and catalytic performance in the wet air oxidation of a spent caustic effluent.

Oil refineries produce annually large quantities of oily sludge and non-biodegradable wastewater during petroleum refining that require adequate management to minimize its environmental impact. The fraction solid of the oily sludge accounts for 25 wt% and without treatment for their valorization. This work is focused on the valorization of these solid particles through their transformation into porous materials with enhanced properties and with potential application in the catalytic wet air oxidation (CWAO) of a non-biodegradable spent caustic refinery wastewater. Hence, dealing with the valorization and treatment of both refinery wastes in a circular approach aligned with the petrol refinery transformations by 2050. The obtained oily sludge carbonaceous materials showed improved surface area (260-762 m2/g) and a high Fe content. The good catalytic performance of these materials in CWAO processes has been attributed to the simultaneous presence of surface basic sites and iron species. Those materials with higher content of Fe and basic sites yielded the highest degradation of organic compounds present in the spent caustic refinery wastewater. In particular, the best-performing material ACT-NP 1.1 (non-preoxidated and thermically treated with 1:1 mass ratio KOH:solid) showed a chemical oxygen demand (COD) removal of 60 % after 3 h of reaction and with a higher degradation rate than that achieved with thermal oxidation without catalyst (WAO) and that using an iron-free commercial activated carbon. Moreover, the biodegradability of the treated wastewater increased up to 80% (from ca. 31% initially of the untreated effluent). Finally, this material was reused up to three catalytic cycles without losing metal species and keeping the catalytic performance.

Intensified-Fenton process for the treatment of phenol aqueous solutions.

An intensified-Fenton process for the treatment of phenol aqueous solutions has been studied as a continuous catalytic wet hydrogen peroxide oxidation system. This process consists of coupling the catalytic activity of a heterogeneous Fenton-like catalyst with the homogeneous contribution of its dissolved iron species. Agglomerated mesoporous SBA-15 silica-supported iron oxide (Fe2O3/SBA-15) material was used as heterogeneous catalyst. The influence of the reaction temperature and the initial hydrogen peroxide dosages was studied in order to minimize the operation cost of the process. The catalytic performance of the process was assessed in terms of total organic carbon (TOC) and hydrogen peroxide conversions. Likewise, the stability of the solid Fenton-like catalyst was also evaluated in terms of the dissolved iron species. The increase of the reaction temperature enhanced the TOC conversion and reduced the iron leaching from the heterogeneous catalyst. These results were related to the degradation of oxalic acid as responsible for iron extraction by formation of soluble stable iron complexes into the aqueous medium. Finally, the use of a moderate hydrogen peroxide concentration (2.6 g/L) and milder temperatures (80-120 °C) has led to remarkable results of TOC and phenol reductions as well as oxidant efficiency through the intensified-Fenton process.

Achieving Discharge Limits in Single-Stage Domestic Wastewater Treatment by Combining Urban Waste Sources and Phototrophic Mixed Cultures.

This work shows the potential of a new way of co-treatment of domestic wastewater (DWW) and a liquid stream coming from the thermal hydrolysis of the organic fraction of municipal solid waste (OFMSW) mediated by a mixed culture of purple phototrophic bacteria (PPB) capable of assimilating carbon and nutrients from the medium. The biological system is an open single-step process operated under microaerophilic conditions at an oxidative reduction potential (ORP) < 0 mV with a photoperiod of 12/24 h and fed during the light stage only so the results can be extrapolated to outdoor open pond operations by monitoring the ORP. The effluent mostly complies with the discharge values of the Spanish legislation in COD and p-values (<125 mg/L; <2 mg/L), respectively, and punctually on values in N (<15 mg/L). Applying an HRT of 3 d and a ratio of 100:7 (COD:N), the presence of PPB in the mixed culture surpassed 50% of 16S rRNA gene copies, removing 78% of COD, 53% of N, and 66% of P. Furthermore, by increasing the HRT to 5 d, removal efficiencies of 83% of COD, 65% of N, and 91% of P were achieved. In addition, the reactors were further operated in a membrane bioreactor, thus separating the HRT from the SRT to increase the specific loading rate. Very satisfactory removal efficiencies were achieved by applying an HRT and SRT of 2.3 and 3 d, respectively: 84% of COD, 49% of N, and 93% of P despite the low presence of PPB due to more oxidative conditions, which step-by-step re-colonized the mixed culture until reaching >20% of 16S rRNA gene copies after 49 d of operation. These results open the door to scaling up the process in open photobioreactors capable of treating urban wastewater and municipal solid waste in a single stage and under microaerophilic conditions by controlling the ORP of the system.

Assessment of Voltage Influence in Carbon Dioxide Fixation Process by a Photo-Bioelectrochemical System under Photoheterotrophy.

Bioelectrochemical systems are a promising technology capable of reducing CO2 emissions, a renewable carbon source, using electroactive microorganisms for this purpose. Purple Phototrophic Bacteria (PPB) use their versatile metabolism to uptake external electrons from an electrode to fix CO2. In this work, the effect of the voltage (from -0.2 to -0.8 V vs. Ag/AgCl) on the metabolic CO2 fixation of a mixed culture of PPB under photoheterotrophic conditions during the oxidation of a biodegradable carbon source is demonstrated. The minimum voltage to fix CO2 was between -0.2 and -0.4 V. The Calvin-Benson-Bassham (CBB) cycle is the main electron sink at these voltages. However, lower voltages caused the decrease in the current intensity, reaching a minimum at -0.8 V (-4.75 mA). There was also a significant relationship between the soluble carbon uptake in terms of chemical oxygen demand and the electron consumption for the experiments performed at -0.6 and -0.8 V. These results indicate that the CBB cycle is not the only electron sink and some photoheterotrophic metabolic pathways are also being affected under electrochemical conditions. This behavior has not been tested before in photoheterotrophic conditions and paves the way for the future development of photobioelectrochemical systems under heterotrophic conditions.

Novel approach for the treatment of the organic fraction of municipal solid waste: Coupling thermal hydrolysis with anaerobic digestion and photo-fermentation.

In this study, two different organic fractions of municipal solid waste (OFMSW) served as raw material in a novel treatment process that combines thermal hydrolysis (TH) pretreatment at different times, followed by anaerobic digestion of the solid fraction and photo-fermentation of the liquid fraction. The results indicate that both wastes performed similarly, and no statistically relevant differences stand out on the overall performance regarding TH times. The thermal pretreatment improves the biodegradability of the solid fraction during anaerobic digestion compensating the loss of the organic matter in the liquid fraction. The produced biogas may feed a combined heat and power (CHP) system, making the process energetically positive in all studied scenarios. In addition, the combination of TH and anaerobic digestion decreased the volume of the waste to be disposed by 59-61%, which is 5-11% higher than that obtained with the traditional treatment of anaerobic digestion process. Specific phototrophic activity tests were performed on the liquid phase using a mixed culture of purple phototrophic bacteria (PPB) that consumed up to 80% of the soluble organics. The assays yielded an average 52% efficiency on specific phototrophic activity (kM) and 62% on biomass yield (YX/S), compared to an optimized growth medium. PPB was also capable of producing polyhydroxyalkanoates, bioH2 and single-cell protein without optimization. Apart from methane, the overall mass balances showed yields up to 150 g of high added-value products per Kg of initial total solids on this proof-of-concept platform.

Resource Recovery Potential From Lignocellulosic Feedstock Upon Lysis With Ionic Liquids.

Lignocellulosic residues from energy crops offer a high potential to recover bioproducts and biofuels that can be used as raw matter for agriculture activities within a circular economy framework. Anaerobic digestion (AD) is a well-established driver to convert these residues into energy and bioproducts. However, AD of lignocellulosic matter is slow and yields low methane potential, and therefore several pre-treatment methods have been proposed to increase the energy yield of this process. Hereby, we have assessed the pre-treatment of lignocellulosic biomass (barley straw) with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate and its effect on the biochemical methane potential (BMP). The BMP of the residue was evaluated at different inoculum to substrate (I/S) ratios and working under meso and thermophilic conditions. Solids destruction upon AD is highly enhanced by the IL-pretreatment. This also resulted in a higher BMP, both in mesophilic as well as thermophilic conditions. At the optimum I/S ratio of 2:1 (dried weight, dw), the BMP of the IL-pre-treated feedstock increased 28 and 80% for 35 days of thermophilic and mesophilic AD, respectively, as compared to the fresh feedstock, achieving values of 364 and 412 LCH4/kgTS. We also explored the effect of this pretreatment on the phosphorus recovery potential from the digestate upon release from the AD process. Thermophilic anaerobic digestion of IL-pre-treated biomass provided the highest P recovery potential from lignocellulosic residues (close to 100% of the theoretical P content of the lignocellulosic feedstock). Therefore, the pretreatment of lignocellulosic feedstock with IL before AD is a promising platform to obtain bioenergy and recover P to be regained for the agriculture sector.