On the modeling and optimization of two-phase olive-oil washing wastewater treatment and polyphenols recovery by ceramic tubular microfiltration membranes.

This research is focused on modelling and optimization of the performance of a 'green procedure' based on microfiltration (MF) technology, for recovery of high added-value antioxidant compounds (TACs) from two-phase olive-oil washing wastewater (OOWW) and its treatment. Concern of olive oil industry to improve the production process in line with Circular Economy is vital to make it respectful with the environment including the management of the generated effluents. Key operational factors of the MF process were studied, modelled and optimized by multifactorial statistical analysis. Box-Behnken design was implemented and data analyzed by ANOVA and interpreted by RSM methodology. MF flux was ulteriorly modelled by a second-grade quadratic fitting equation comprising the significant operating variables, being them pressure and tangential velocity. Optimized flow achieved 10962.4 L/hm2 at 8.5 bar, 4.2 L/min tangential velocity, ambient temperature (25 °C) and raw pH (5.13). Finally, multiple-response permitted to optimize up to 67% TSS rejection and minimum rejection of TACs of 22.9%, upon 3.57 bar, 4.2 m/s, 23.4 °C and effluent pH of 5.1, meaning the recovery of 77.1% of TACs from OOWW in the permeate stream, up to 1207.1 mg/L. Results show that the proposed process allows a reduction in energy consumption by using the raw effluent with unmodified pH and ambient temperature.

Enhanced biomethane production by co-digestion of mixed sewage sludge and dephenolised two-phase olive pomace.

In this study, co-digestion of mixed sewage sludge from a wastewater treatment plant (WWTP) and partially dephenolised two-phase olive pomace (DOP) as a co-substrate was addressed with the aim of improving the biodigestibility of both substrates. The introduction of DOP into WWTP anaerobic digester facilities could significantly increase biomethane production and enhance the sustainability of both activities. An improvement in the system's performance was supported by stability parameters: total alkalinity increased and stabilised with the addition of 5% v/v DOP, and the specific energy loading rate was maintained at 0.177 ± 0.03 d-1, which indicated better buffer capacity and stability in the bioreactor, and the possibility of enhancing the organic loading rate. In terms of average daily biogas production rate, an increase of 39% was achieved, up to 0.39 ± 0.11 L L-1d-1. Moreover, there was a 40% and 37% improvement in specific methane production and methane production rate, respectively, up to 0.28 ± 0.02 L CH4 g TVS-1 and 0.26 ± 0.08 L L-1d-1. In addition, the proposed strategy leads to an energy saving of 20,328.6 kWh year-1 at the WWTP as a result of the electric energy production surplus, corresponding to an annual saving of €3293.23.

Effect of operating parameters on the physical and chemical stability of an oil gelled-in-water emulsified curcumin delivery system.

BACKGROUND: Curcumin is a natural antioxidant with important beneficial properties for health, although its low bioavailability and sensitivity to many environmental agents limits its use in the food industry. Furthermore, some studies mention a potential synergistic effect with omega-3 polyunsaturated fatty acids, comprising other bioactive compounds extremely unstable and susceptible to oxidation. A relatively novel strategy to avoid oxidation processes is to transform liquid oils into three-dimensional structures by adding a gelling agent and forming a self-assembled network that can later be vectorized by incorporating it into other systems. The present study aimed to design and optimize an oil gelled-in-water curcumin-loaded emulsion to maximize curcumin stability and minimize lipid oxidation in terms of some critical operating parameters, such as dispersed phase, emulsifier and stabilizer concentrations, and homogenization rate. RESULTS: The operating conditions that had a significant effect on the formulation were the dispersed phase weight fraction affecting droplet size and total lipid oxidation, homogenization conditions affecting droplet size and primary lipid oxidation, and emulsifier concentration affecting droplet size (significance level = 95%). The optimal formulation for maximizing curcumin load and minimizing lipid oxidation in the oleogelified matrix was 140.4 g kg-1 dispersed phase, 50.0 g kg-1 emulsifier, 4.9 g kg-1 stabilizer and homogenization speed 1016 × g. CONCLUSION: The results obtained in the present study provide a valuable tool for the rational design and development of oil gelled-in-water emulsions that stabilize and transport bioactive compounds such as curcumin. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

ZnO Nano-Particles Production Intensification by Means of a Spinning Disk Reactor.

Zinc Oxide is widely used in many industrial sectors, ranging from photocatalysis, rubber, ceramic, medicine, and pigment, to food and cream additive. The global market is estimated to be USD 3600M yearly, with a global production of 10 Mt. In novel applications, size and shape may sensibly increase the efficiency and a new nano-ZnO market is taking the lead (USD 2000M yearly with a capacity of 1 Mt and an expected Compound Annual Growth Rate of 20%/year). The aim of this work was to investigate the possibility of producing zinc oxide nanoparticles by means of a spinning disk reactor (SDR). A lab-scale spinning disk reactor, previously used to produce other nanomaterials such as hydroxyapatite or titania, has been investigated with the aim of producing needle-shaped zinc oxide nanoparticles. At nanoscale and with this shape, the zinc oxide particles exhibit their greatest photoactivity and active area, both increasing the efficiency of photocatalysis and ultraviolet (UV) absorbance. Working at different operating conditions, such as at different disk rotational velocity, inlet distance from the disk center, initial concentration of Zn precursor and base solution, and inlet reagent solution flowrate, in certain conditions, a unimodal size distribution and an average dimension of approximately 56 nm was obtained. The spinning disk reactor permits a continuous production of nanoparticles with a capacity of 57 kg/d, adopting an initial Zn-precursor concentration of 0.5 M and a total inlet flowrate of 1 L/min. Product size appears to be controllable, and a lower average dimension (47 nm), adopting an initial Zn-precursor concentration of 0.02 M and a total inlet flow-rate of 0.1 L/min, can be obtained, scarifying productivity (0.23 kg/d). Ultimately, the spinning disk reactor qualifies as a process-intensified equipment for targeted zinc oxide nanoparticle production in shape in size.

Analysis of the Flux Performance of Different RO/NF Membranes in the Treatment of Agroindustrial Wastewater by Means of the Boundary Flux Theory.

Dynamic membrane system behaviour must be adequately addressed to avoid process unfeasibility. The lack of proper analysis will mean relying on erroneous permeate flux values in the system design, which will lead to quick and/or steady high fouling rates. In this paper, the authors present additional data supporting the boundary flux theory as a helpful tool for membrane engineers to carefully avoid process failures. By fitting the dynamic permeate flux data to the boundary flux model, it was possible to calculate the ß fouling index for the three selected membranes (one nanofiltration (NF) and two reverse osmosis (RO) ones). The dynamic flux given by the low-pressure RO membrane did not follow sub-boundary operating conditions, since a sharp flux loss was measured throughout the whole operating cycle, pinpointing that supra-boundary flux conditions were governing the system. This was supported by the calculated value of the ß fouling parameter, which resulted to be in the order of ten times higher for this membrane. However, the values of ß→0 for the SC-RO and DK-NF ones, supported by the very low value of the sub-boundary fouling parameter α (0.002 and 0.007 L·h-1·m-2·bar-2, respectively), ensure nearly boundary operating conditions for these membranes.

Operation setup of a nanofiltration membrane unit for purification of two-phase olives and olive oil washing wastewaters.

In this research work, the purification of olives and olive oil washing wastewaters from two-phase extraction mills by a novel polymeric NF membrane is addressed. The effluent was previously subjected to a physicochemical secondary-tertiary treatment previously optimized at pilot and industrial scales. Within the adequate operating conditions, suspended solids could be completely removed, and the EC was considerable lowered down to good quality values acceptable for irrigation purposes (1.9-2.0mScm-1), whereas the chemical oxygen demand was reduced below 31.9mgL-1. The standards for discharging in public waterways or reusing the final treated effluent for irrigation with acceptable quality were therefore accomplished. Moreover, the performance of the NF membrane ranged between 2.82 and 6.96Lh-1m-2bar-1, that is, a flux of up to 160Lh-1m-2 at 25bar. Furthermore, the 15-minute acid cleaning plus 15-minute alkaline/detergent cleaning could recover satisfactorily the permeability of the membrane. The necessary overdesign of the membrane operation was estimated as 9.42-17.53%, which meant a maximum required membrane area of 61.82m2. Hence, just 2 membrane modules should be implemented in a medium-sized mill to engineer the operation, boosting the economic feasibility of the proposed process both from operational and capital costs point of views.

Control systems for olive mill wastewater treatment with ultrafiltration and nanofiltration membrane in series based on the boundary flux theory.

Proper membrane process design can be a difficult task to accomplish when fouling is present, and must be faced. Engineers usually consider the project variables concerning productivity and selectivity and follow these targets. However, in the presence of fouling, additional parameters must be considered, implying better knowledge of fouling phenomena. One possible solution to increase the reliability of a process is the use of stable control systems. This article reports a suitable method to reach this target, based on the boundary flux theory. The knowledge of the boundary flux values permits avoidance of high fouling operating conditions on a selected membrane. The goal here was to determine the framework for control of an ultrafiltration (UF) and nanofiltration (NF) batch membranes-in-series process treatment for olive mill wastewater, relying on these boundary flux points, which will thereafter serve for the automatic control of the process by an advanced control system. In this work, boundary flux values equal to 10 L h-1 m-2 for the UF membrane module and 14.3 L h-1 m-2 for the NF one were estimated. Moreover, the membrane constant permeability loss, measured by integrating the sub-boundary fouling index, was estimated to be reduced in the order of 65.4% for the NF membrane after the applied pretreatment and UF. This strategy permitted attaining stable and constant productivity for both membranes. Moreover, it is shown that, relying on the boundary flux modelization, both types of control systems (feed control and pressure control) could be used reliably. The proposed approach could help safely narrow the overdesign of membrane processes due to fouling issues and thus would have an impact on the reduction of the costs for both membrane processes.

On Operating a Nanofiltration Membrane for Olive Mill Wastewater Purification at Sub- and Super-Boundary Conditions.

In the last decades, membrane processes have gained a significant share of the market for wastewater purification. Although the product (i.e., purified water) is not of high added value, these processes are feasible both technically and from an economic point of view, provided the flux is relatively high and that membrane fouling is strongly inhibited. By controlling membrane fouling, the membrane may work for years without service, thus dramatically reducing operating costs and the need for membrane substitution. There is tension between operating at high permeate fluxes, which enhances fouling but reduces capital costs, and operating at lower fluxes which increases capital costs. Operating batch membrane processes leads to increased difficulties, since the feed fed to the membrane changes as a function of the recovery value. This paper is concerned with the operation of such a process. Membrane process designers should therefore avoid membrane fouling by operating membranes away from the permeate flux point where severe fouling is triggered. The design and operation of membrane purification plants is a difficult task, and the precision to properly describe the evolution of the fouling phenomenon as a function of the operating conditions is a key to success. Many reported works have reported on the control of fouling by operating below the boundary flux. On the other hand, only a few works have successfully sought to exploit super-boundary operating conditions; most super-boundary operations are reported to have led to process failures. In this work, both sub- and super-boundary operating conditions for a batch nanofiltration membrane process used for olive mill wastewater treatment were investigated. A model to identify a priori the point of transition from a sub-boundary to a super-boundary operation during a batch operation was developed, and this will provide membrane designers with a helpful tool to carefully avoid process failures.

On the Recent Use of Membrane Technology for Olive Mill Wastewater Purification.

Many reclamation treatments as well as integrated processes for the purification of olive mill wastewaters (OMW) have already been proposed and developed but not led to completely satisfactory results, principally due to complexity or cost-ineffectiveness. The olive oil industry in its current status, composed of little and dispersed factories, cannot stand such high costs. Moreover, these treatments are not able to abate the high concentration of dissolved inorganic matter present in these highly polluted effluents. In the present work, a review on the actual state of the art concerning the treatment and disposal of OMW by membranes is addressed, comprising microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO), as well as membrane bioreactors (MBR) and non-conventional membrane processes such as vacuum distillation (VD), osmotic distillation (OD) and forward osmosis (FO). Membrane processes are becoming extensively used to replace many conventional processes in the purification of water and groundwater as well as in the reclamation of wastewater streams of very diverse sources, such as those generated by agro-industrial activities. Moreover, a brief insight into inhibition and control of fouling by properly-tailored pretreatment processes upstream the membrane operation and the use of the critical and threshold flux theories is provided.

Impacts of operating conditions on nanofiltration of secondary-treated two-phase olive mill wastewater.

In the present paper, a thin-film composite polymeric nanofiltration (NF) membrane is examined for the tertiary treatment of secondary-treated two-phase olive mill wastewater, in substitution of the reverse osmosis membrane used in previous work by the Authors. Overcoming the deleterious fouling phenomena persistently encountered in membrane processes managing wastewater streams was indeed pursued. Setting the adequate parameters of the operating variables - that is, operating at ambient temperature upon a net pressure equal to 13 bar (Pc), tangential crossflow in the order of 2.55 m s(-1) to attain enough turbulence over the membrane, and above the point of zero charge (pH > 5.8) of the membrane - ensured high steady-state permeate productivity (59.6 L h(-1) m(-2)), also economically sustainable in time owed to minimization of the fouling-build up rate (0.91 h(-1)). Moreover, these conditions also provided high feed recovery (90%) and significant rejection efficiencies for the electroconductivity (58.1%) and organic matter (76.1%). This led to a purified permeate stream exiting the NF membrane operation exhibiting average EC and COD values equal to 1.4 mS cm(-1) and 45 mg L(-1). This permits complying with the water quality parameters established by different regulations for discharge public waterways and irrigation purposes.

Physicochemical analysis and adequation of olive oil mill wastewater after advanced oxidation process for reclamation by pressure-driven membrane technology.

Physicochemical characterization of olive mill wastewaters (OMW) was studied after a primary and secondary treatment was implemented in an olive oil factory in Jaén (Spain), comprising natural precipitation, Fenton-like reaction, flocculation-sedimentation and olive stone filtration in series. The application of membrane technology in improving the quality of the secondary-treated OMW (OMW/ST) was examined, to reduce the hazardous electroconductivity (EC) values (2-3 mS cm(-1)). Particle size distribution on OMW/ST shows supra-micron colloids and suspended solids as well as sub-micron particles with a mean size below 1.5 µm remaining in considerable concentration. The high organic pollutants percentage (31.7%) registered with an average diameter below 3 kDa is sensibly relevant for membrane fouling. Mesophilic aerobic bacteria growth warns of possible membrane biofouling formation. The saturation index indicates to work upon recovery factor below 90%. Finally, operating at a pressure equal to 15 bar ensured low fouling and high flux production on the selected NF membrane (69.9 L h(-1)m(-2)) and significant rejection efficiencies (55.5% and 88.5% for EC and COD). This permits obtaining an effluent with good quality according to the recommendations of the Food and Agricultural Association (FAO) with the goal of reusing the regenerated water for irrigation.

About merging threshold and critical flux concepts into a single one: the boundary flux.

In the last decades much effort was put in understanding fouling phenomena on membranes. One successful approach to describe fouling issues on membranes is the critical flux theory. The possibility to measure a maximum value of the permeate flux for a given system without incurring in fouling issues was a breakthrough in membrane process design. However, in many cases critical fluxes were found to be very low, lower than the economic feasibility of the process. The knowledge of the critical flux value must be therefore considered as a good starting point for process design. In the last years, a new concept was introduced, the threshold flux, which defines the maximum permeate flow rate characterized by a low constant fouling rate regime. This concept, more than the critical flux, is a new practical tool for membrane process designers. In this paper a brief review on critical and threshold flux will be reported and analyzed. And since the concepts share many common aspects, merged into a new concept, called the boundary flux, the validation will occur by the analysis of previously collected data by the authors, during the treatment of olive vegetation wastewater by ultrafiltration and nanofiltration membranes.

Performance modeling and cost analysis of a pilot-scale reverse osmosis process for the final purification of olive mill wastewater.

A secondary treatment for olive mill wastewater coming from factories working with the two-phase olive oil production process (OMW-2) has been set-up on an industrial scale in an olive oil mill in the premises of Jaén (Spain). The secondary treatment comprises Fenton-like oxidation followed by flocculation-sedimentation and filtration through olive stones. In this work, performance modelization and preliminary cost analysis of a final reverse osmosis (RO) process was examined on pilot scale for ulterior purification of OMW-2 with the goal of closing the loop of the industrial production process. Reduction of concentration polarization on the RO membrane equal to 26.3% was provided upon increment of the turbulence over the membrane to values of Reynolds number equal to 2.6 × 104. Medium operating pressure (25 bar) should be chosen to achieve significant steady state permeate flux (21.1 L h-1 m-2) and minimize membrane fouling, ensuring less than 14.7% flux drop and up to 90% feed recovery. Under these conditions, irreversible fouling below 0.08 L h-2 m-2 bar-1 helped increase the longevity of the membrane and reduce the costs of the treatment. For 10 m3 day-1 OMW-2 on average, 47.4 m2 required membrane area and 0.87 € m-3 total costs for the RO process were estimated.

A novel photocatalyst with ferromagnetic core used for the treatment of olive oil mill effluents from two-phase production process.

Photocatalytic degradation of olive oil mill wastewater from two-phase continuous centrifugation process was studied. A novel photocatalyst with ferromagnetic properties was characterized and investigated. The degradation capacity of the photocatalytic process of olive oil washing wastewater (OMW) and mixture of olives and olive oil (1 v/v) washing wastewaters (MOMW) was demonstrated. At lab-scale, the %COD removal and residence time (τ) for MOMW and OMW were 58.4% (τ = 2 h) and 21.4% (τ = 3 h), respectively. On the other hand, at pilot scale, 23.4% COD(removal), 19.2% total phenols(removal), and 28.1% total suspended solids(removal) were registered at the end of the UV/TiO2 process for OMW, whereas 58.3% COD(removal), 27.5% total phenols(removal), and 25.0% total suspended solids(removal) for MOMW. Also, before the UV/TiO2 reaction, a pH-T flocculation operation as pretreatment was realized. The overall efficiency of the treatment process for MOMW was up to 91% of COD(removal), in contrast with 33.2% of COD(removal) for OMW.