Red Fruit Juice Concentration by Osmotic Distillation: Optimization of Operating Conditions by Response Surface Methodology.

Osmotic distillation (OD) was implemented at laboratory scale to concentrate a red fruit juice produced from a blend of blood orange, prickly pear, and pomegranate juice. The raw juice was clarified by microfiltration and then concentrated by using an OD plant equipped with a hollow fiber membrane contactor. The clarified juice was recirculated on the shell side of the membrane module, while calcium chloride dehydrate solutions, used as extraction brine, were recirculated on the lumen side in a counter-current mode. The influence of different process parameters, such as brine concentration (20, 40, and 60% w/w), juice flow rate (0.3, 2.0, and 3.7 L min-1), and brine flow rate (0.3, 2.0, and 3.7 L min-1) on the performance of the OD process in terms of evaporation flux and increase in juice concentration, was investigated according to the response surface methodology (RSM). From the regression analysis, the evaporation flux and juice concentration rate were expressed with quadratic equations of juice and brine flow rates, as well as the brine concentration. The desirability function approach was applied to analyse the regression model equations in order to maximize the evaporation flux and juice concentration rate. The optimal operating conditions were found to be 3.32 L min-1 brine flow rate, 3.32 L min-1 juice flow rate, and an initial brine concentration of 60% w/w. Under these conditions, the average evaporation flux and the increase in the soluble solid content of the juice resulted in 0.41 kg m-2 h-1 and 12.0 °Brix, respectively. Experimental data on evaporation flux and juice concentration, obtained in optimized operating conditions, resulted in good agreement with the predicted values of the regression model.

The Optimization of Operating Conditions in the Cross-Flow Microfiltration of Grape Marc Extract by Response Surface Methodology.

The recovery of valuable compounds like phenolic compounds and sugars from grape marc extracts implies different steps, including clarification. In this study, a response surface methodology (RSM) was used as a statistical tool to study the effects of operating conditions such as transmembrane pressure (TMP), temperature and feed flow rate on the performance of a microfiltration (MF) monotubular ceramic membrane with a pore size of 0.14 µm in the clarification of grape marc extract from the Carménère variety, as well to optimize the process conditions by implementing the Box-Behnken statistical design. The desirability function approach was applied to analyze the regression model equations in order to maximize the permeate flux and concentration of malvidin-3-O-glucoside, glucose and fructose in the clarified extract. The optimal operating conditions were found to be 1 bar, 29.01 °C and 5.64 L/min. Under these conditions, the permeate flux and concentration of malvidin-3-O-glucoside, glucose and fructose resulted in 65.78 L/m2h, 43.73 mg/L, 305.89 mg/L, and 274.85 mg/L, respectively.

Prediction of Permeate Flux in Ultrafiltration Processes: A Review of Modeling Approaches.

In any membrane filtration, the prediction of permeate flux is critical to calculate the membrane surface required, which is an essential parameter for scaling-up, equipment sizing, and cost determination. For this reason, several models based on phenomenological or theoretical derivation (such as gel-polarization, osmotic pressure, resistance-in-series, and fouling models) and non-phenomenological models have been developed and widely used to describe the limiting phenomena as well as to predict the permeate flux. In general, the development of models or their modifications is done for a particular synthetic model solution and membrane system that shows a good capacity of prediction. However, in more complex matrices, such as fruit juices, those models might not have the same performance. In this context, the present work shows a review of different phenomenological and non-phenomenological models for permeate flux prediction in UF, and a comparison, between selected models, of the permeate flux predictive capacity. Selected models were tested with data from our previous work reported for three fruit juices (bergamot, kiwi, and pomegranate) processed in a cross-flow system for 10 h. The validation of each selected model's capacity of prediction was performed through a robust statistical examination, including a residual analysis. The results obtained, within the statistically validated models, showed that phenomenological models present a high variability of prediction (values of R-square in the range of 75.91-99.78%), Mean Absolute Percentage Error (MAPE) in the range of 3.14-51.69, and Root Mean Square Error (RMSE) in the range of 0.22-2.01 among the investigated juices. The non-phenomenological models showed a great capacity to predict permeate flux with R-squares higher than 97% and lower MAPE (0.25-2.03) and RMSE (3.74-28.91). Even though the estimated parameters have no physical meaning and do not shed light into the fundamental mechanistic principles that govern these processes, these results suggest that non-phenomenological models are a useful tool from a practical point of view to predict the permeate flux, under defined operating conditions, in membrane separation processes. However, the phenomenological models are still a proper tool for scaling-up and for an understanding the UF process.

Recovery of Anthocyanins and Monosaccharides from Grape Marc Extract by Nanofiltration Membranes.

Wastewaters and by-products generated in the winemaking process are important and inexpensive sources of value-added compounds that can be potentially reused for the development of new products of commercial interest (i.e., functional foods). This research was undertaken in order to evaluate the potential of nanofiltration (NF) membranes in the recovery of anthocyanins and monosaccharides from a clarified Carménère grape marc obtained through a combination of ultrasound-assisted extraction and microfiltration. Three different flat-sheet nanofiltration (NF) membranes, covering the range of molecular weight cut-off (MWCO) from 150 to 800 Da, were evaluated for their productivity as well as for their rejection towards anthocyanins (malvidin-3-O-glucoside, malvidin 3-(acetyl)-glucoside, and malvidin 3-(coumaroyl)-glucoside) and sugars (glucose and fructose) in selected operating conditions. The selected membranes showed differences in their performance in terms of permeate flux and rejection of target compounds. The NFX membrane, with the lowest MWCO (150-300 Da), showed a lower flux decay in comparison to the other investigated membranes. All the membranes showed rejection higher than 99.42% for the quantified anthocyanins. Regarding sugars rejection, the NFX membrane showed the highest rejection for glucose and fructose (100 and 92.60%, respectively), whereas the NFW membrane (MWCO 300-500 Da) was the one with the lowest rejection for these compounds (80.57 and 71.62%, respectively). As a general trend, the tested membranes did not show a preferential rejection of anthocyanins over sugars. Therefore, all tested membranes were suitable for concentration purposes.

An Experimental Study of Membrane Contactor Modules for Recovering Cyanide through a Gas Membrane Process.

Cyanide is one of the main reagents used in gold mining that can be recovered to reduce operational costs. Gas membrane technology is an attractive method for intensifying both the stripping and absorption processes of valuable compounds, such as cyanide. However, scaling-up this technology from laboratory to industry is an unsolved challenge because it requires the improvement of the experimental methodologies that replicate lab-scale results at a larger scale. With this purpose in mind, this study compares the performance of three different hollow fiber membrane contactor modules (1.7 × 5.5 Mini Module, 1.7 × 10 Mini Module, and 2.5 × 8 Extra Flow). These are used for recovering cyanide from aqueous solutions at laboratory scale, using identical operational conditions. For each experimental set-up, mass-transfer correlations at the ranges of feed flows assayed were determined. The modules with the smallest and largest area of mass transfer reached similar cyanide recoveries (>95% at 60 min), which demonstrate the impact of module configuration on their operating performance. The results obtained here are limited for scaling-up the membrane module performance only because operating modules with the largest area results in a low Re number. This fact limits the extrapolation of results from the mass-transfer correlation.

Recent advances and perspectives of ultrasound assisted membrane food processing.

Power ultrasound (US) transmits substantial amounts of small mechanical movements serving for particle detaching in membrane filtrations. This topic has been reviewed in recent years mainly focused on the mechanisms by which the flux is improved under specific processing conditions. US also been shown to improve food quality by changing physical properties and modifying the activity of enzymes and microorganisms. Surprisingly, limited information exists regarding on how the application of US results in terms of process and quality during membrane filtration of complex matrices such as liquid foods. This review highlights the recent advances in the use of US in membrane filtration processes focused in the manufacturing of foodstuffs and food ingredients, and perspectives of novel hybrid membrane-US systems that may be quite interesting for this field. The application of US in food membrane processing increases the flux, but the lack of standardization regarding to experimental conditions, make suitable comparisons impossible. In this sense, careful attention must be paid regarding to the ultrasonic intensity (UI), the membrane configuration and type of transducers and volume of the treated solution. Dairy products are the most studied application of US membrane food processing, but research has been mainly focused on flux enhancement; hitherto there have been no reports of how operational variables in these processes affect critical aspects such as quality and food safety. Also, studies performed at industrial scale and economical assessments are still missing. Application of US combined with membrane operations such as reverse osmosis (RO), forward osmosis (FO) and enzyme membrane bioreactors (EMBR) may result interesting for the production of value-added foods. In the perspective of the authors, the stagnation of the development of acoustic filtration systems in food is due more to a prejudice on this subject, rather than actual impedance due to the lack of technological development of transducers. This later has shown important advances in the last years making them suitable for tailor made applications, thus opening several research opportunities to the food engineering not yet explored.

Impact of Membrane Pore Size on the Clarification Performance of Grape Marc Extract by Microfiltration.

The influence of membrane pore size on the permeate flux, fouling mechanism, and rejection of soluble and suspended solids, as well as of phenolics and anthocyanins, in the clarification of grape marc extract by microfiltration (MF) was studied. MF was operated by using three monotubular ceramic membranes with a pore size of 0.14, 0.2, and 0.8 µm, respectively, according to a batch concentration configuration in selected operating conditions (2.25 bar as operating pressure, 4.93 L/min as feed flow rate, and 25 °C as operating temperature). No significant differences in the permeate flux values were appreciated despite the difference in pore size. The mathematical analyses of the flux behavior revealed that intermediate pore blocking is the predominant mechanism for 0.14 and 0.2 µm membranes, whereas complete pore blocking prevails for the 0.8 µm membrane. Differences in the fouling mechanism were associated with differences in the total phenols rejection: the highest rejection was observed for the 0.8 µm membrane followed by 0.2 and 0.14 µm membranes. All selected membranes showed low rejection of sugars, with values lower than 10%, and no retention towards anthocyanins. All the clarified extracts showed a turbidity lower than 4.87 NTU. Based on the experimental results, the 0.14 µm membrane appeared as the best option for the clarification of grape marc extract.

Interaction of H2O with (CuS)n, (Cu2S)n, and (ZnS)n small clusters (n = 1-4, 6): relation to the aggregation characteristics of metal sulfides at aqueous solutions.

The interaction of H2O onto small CuS, Cu2S, and ZnS clusters was theoretically studied by Density Functional Theory computations to get insights into the aggregation characteristics of metal sulfides at aqueous solutions. The results show the charge-controlled interactions with polarized solvent molecules are favored on the ZnS clusters compared with CuS and Cu2S clusters. Moreover, the chemical adsorption of H2O molecules is energetically favored onto ZnS clusters with higher interaction energies of up to 35.4 kcal/mol compared with CuS and Cu2S clusters (up to 31.3 kcal/mol), where the stability of H2O adsorption decreases as the size of the clusters increases. However, thermochemical analysis shows that the adsorption of H2O on copper sulfides is not a spontaneous process at room temperature. Additionally, the electrostatic energy of H2O onto the Cu2S and CuS clusters is lower than that associated with the H2O-H2O interactions, suggesting that copper precipitates prefer to bind between them at early stages of the precipitation process due to an unfavorable solvent-solute interaction. Dispersion forces play a relative key role in the interaction of water on copper sulfides, while for zinc sulfide clusters, the adsorption energy is slightly influenced by dispersion contributions. Accordingly, the aggregation of zinc sulfides in a water environment is expected to be lower compared with copper sulfides, and where the aggregation characteristics are not determined by the binding energy of the sulfides, but of the ability to interact with the solvent molecules. These statements were confirmed by experimental optical microscopy analysis and settling tests during precipitation processes in water. Therefore, this work allows proposing a simple strategy to study the aggregation characteristics of metal sulfides, which turns useful for use in hydrometallurgical applications.

Nanofiltration and Tight Ultrafiltration Membranes for the Recovery of Polyphenols from Agro-Food By-Products.

Pressure-driven membrane-based technologies represent a valid approach to reduce the environmental pollution of several agro-food by-products. Recently, in relation to the major interest for natural compounds with biological activities, their use has been also addressed to the recovery, separation and fractionation of phenolic compounds from such by-products. In particular, tight ultrafiltration (UF) and nanolfiltration (NF) membranes have been recognized for their capability to recover phenolic compounds from several types of agro-food by-products. The separation capability of these membranes, as well as their productivity, depends on multiple factors such as membrane material, molecular weight cut-off (MWCO) and operating conditions (e.g., pressure, temperature, feed flow rate, volume reduction factor, etc.). This paper aims at providing a critical overview of the influence of these parameters on the recovery of phenolic compounds from agro-food by-products by using tight UF and NF membranes. The literature data are analyzed and discussed in relation to separation processes, molecule properties, membrane characteristics and other phenomena occurring in the process. Current extraction methodologies of phenolic compounds from raw materials are also introduced in order to drive the implementation of integrated systems for the production of actractive phenolic formulations of potential interest as food antioxidants.

Recovery of flavonoids from orange press liquor by an integrated membrane process.

Orange press liquor is a by-product generated by the citrus processing industry containing huge amounts of natural phenolic compounds with recognized antioxidant activity. In this work, an integrated membrane process for the recovery of flavonoids from orange press liquors was investigated on a laboratory scale. The liquor was previously clarified by ultrafiltration (UF) in selected operating conditions by using hollow fiber polysulfone membranes. Then, the clarified liquor with a total soluble solids (TSS) content of 10 g·100 g-1 was pre-concentrated by nanofiltration (NF) up to 32 g TSS 100 g-1 by using a polyethersulfone spiral-wound membrane. A final concentration step, up to 47 g TSS 100 g-1, was performed by using an osmotic distillation (OD) apparatus equipped with polypropylene hollow fiber membranes. Suspended solids were completely removed in the UF step producing a clarified liquor containing most part of the flavonoids of the original press liquor due to the low rejection of the UF membrane towards these compounds. Flavanones and anthocyanins were highly rejected by the NF membrane, producing a permeate stream with a TSS content of 4.5 g·100 g-1. An increasing of both the flavanones and anthocyanins concentration was observed in the NF retentate by increasing the volume reduction factor (VRF). The final concentration of flavonoids by OD produced a concentrated solution of interest for nutraceutical and pharmaceutical applications.