Effect of carboxymethylcellulose on potassium bitartrate crystallization on model solution and white wine

Instability in bottled wines refer to tartaric salts crystallization such as potassium bitartrate (KHT). It is not desirable as consumers see the settled salts as an evidence of a poor quality control. In some cases, it causes excessive gushing in sparkling wine. We investigate the effect of two oenological carboxymethylcellulose (CMC) for KHT inhibition in a model solution of white wine by studying the impact of some properties of CMC such as the degree of polymerization, the degree of substitution, and the apparent dissociation constant determined by potentiometric titration. Polyelectrolyte adsorption is used for determining the surface and total charge and for providing information about the availability of CMC charged groups for interacting with KHT crystal faces. The inhibitory efficiency of CMC on model solution is evaluated by measuring the induction time with the help of conductimetric methods. Crystals growth with and without CMC are studied by observation with MEB and by thermal analysis using DSC. The results confirm the effectiveness of CMC as an inhibitor of KHT crystallization in a model solution. The main hypothesis of the mechanism lies in the interaction of dissociated anionic carboxymethyl groups along the cellulose backbone with positively charged layers on KHT faces like the {0 1 0} face. Key factors such as pH, CMC chain length and total charge are discusse

Analysis of membrane fouling during cross-flow microfiltration of wine

The aim of this study was to investigate the individual impact on wine molecules as tannins, pectins and mannoproteins on multichannel ceramic membrane fouling during wine cross-flow microfiltration. The characterization of fouling mechanisms involved in the previous filtrations was realized by using the classical fouling models and the analysis of the total resistance curves. It was shown that the obtained initial fluxes are dependant of the nature of the studied molecules and their concentration. According to their increasing effect on permeate flux decline, the studied wine components could be ranked as: mannoproteins < tannins < pectins. During the filtration of wine added with tannins, it was found that the filtrations were governed by the cake layer formation mechanism. The presence of pectins caused the formation of gel-type layer which is found to be compressible under high pressures. For wines added with mannoprotein filtrations, it was shown that there is a threshold concentration above which a plateau value of permeate flux is obtained. Industrial relevance: The cross-flow microfiltration applied to wine filtration has become a legitimate alternative to conventional filtration processes. However, membrane fouling which affects the operating costs and the plant maintenance, limits the widespread application of this technique. To avoid or reduce membrane fouling, it is extremely important to identify the fouling elements and the mechanisms that govern the process. A better understanding of the mechanisms whereby fouling is formed during wine microfiltration may lead to be in position to control fouling or reduce it, to improve cleaning procedures and to adapt the process to the product to be filtered. The results presented in this paper concern the investigation and the understanding of fouling mechanisms by wine colloids (tannins, pectins and mannoproteins). We found that wine colloids had a strong impact on membrane fouling. Independently of their concentrations found in wine, they can be ranked according to their increasing effect on permeate flux as: mannoproteins b tannins b pectins. Such result provides important information and a better vision on the methods which can be used to limit membrane fouling for example the use of pectinolytic enzymes before filtration in order to hydrolyze pectin chains or precipitation of unstable tannins by finning the wine with bentonite. By elucidating fouling mechanisms such as cake layer and gel type layer, we can adapt the hydrodynamic process to control membrane fouling

Cross-flow microfiltration applied to oenology: A review

The cross-flow microfiltration applied to wine filtration has become a legitimate alternative to conventional filtration processes. However, membrane fouling which affects the operating costs and the plant maintenance, limits the widespread application of this technique. The aim of this review is to provide a better understanding of the development of the cross-flow microfiltration in wine industry, as well as the complexity of wine composition and its consequences on membrane fouling. This review covers also the impact of the operating conditions and the membrane characteristics on fouling mechanisms. Strategies to limit fouling as well as the latest innovations and commercial proposal are discussed in this paper

Intensification of Ester Production in a Continuous Reactor

Numerous continuous intensified reactors are now accessible on the market that offer enhanced thermal performances in a continuous reactor. Such reactors are then particularly suited to fast and highly exothermic reactions. In this paper, the ability to also manage a slow and equilibrated system, the methyl acetate esterification reaction, on condition of intensification in terms of design and operating conditions is presented. To achieve this purpose, a new kinetics model has been developed and validated from experiments carried out in a lab scale batch reactor. Implemented in a simulation framework, this model leads to an intensified design of the reactor and the associated operating conditions. All this intensification methodology has been supported and validated by experimental studies

Impact of the physico-chemistry of the wine on membrane filtration performance

During the process of wine making, operation of cross-flow microfiltration allows a one-step clarification and sterilization of wine, with lower waste compared to the conventional processes of clarification and sterilization. Indeed, these processes are sources of voluminous waste (earth, Kieselguhr, additives), when discharges are becoming more and more restricted by environmental and health rules. Nevertheless, cross-flow microfiltration of wine presents a major drawback: membrane fouling causes a significant decrease in the flow rates, due to excessive retention of some wine components which could lead ultimately to the alteration of the quality of wine. The aim of this work was to study the impact of some specific wine components (phenolic compounds and yeast extract), as well as some physico-chemical parameters (pH) in regard to membrane fouling. Studies were performed using one red wine and synthetic wines, using cellulose acetate membranes (0.2 μm) operated in the dead-end mode under 2 bar pressure. The simultaneous presence of the both species of phenolic compounds (anthocyanins and tannins) in the synthetic wine was shown to be the main cause of fouling, whereas the presence of one specie leads only to standard blocking type behavior. An important decrease in the flow rates was also observed when yeast extract was added to the liquid. This yeast extract was shown to contain 300 mg/g of proteins and to be free of mannoproteins. The influence of these proteins on fouling was demonstrated while pre-treating the synthetic wine with bentonite, which was able to adsorb proteins, and in this case, no fouling was observed. It was also shown that, when decreasing the pH, the flow rate was enhanced. For all experiments, a fouling index or cake specific resistance, according to the type of fouling, was calculated in order to be used as a reference to estimate the filterability of a given wine, according to its composition in some targeted molecules. Finally, the experiments of the actual red wine exhibited complete rapid fouling of the membrane, probably due to the presence of high concentration of phenolic compounds

Hydrodynamic study of a monolith-type reactor for intensification of gas-liquid applications

Two-phase monolith-type reactors allow intensified heat and mass transfer rates, but often suffer from fluid maldistribution and undesired flow regimes in channels. A cold-flow monolith reactor (0.1 m diameter, 84 channels) is used here to assess liquid distribution and flow regimes at various air and water velocities: resistive probes give an insight of the flow patterns within 5 representative channels located at different radial positions, showing that regime transition to Taylor flow occurs in these channels simultaneously at lower gas and liquid superficial velocities than predicted by single capillary studies (namely uL and uG < 0.1 m s−1). nA full mapping of the partial liquid flow rates in the monolith channels is derived by a gravimetric method via specifically designed collectors. In the identified Taylor flow domain, liquid distribution exhibits a W-shaped profile with marked peaks at low liquid velocity (uL = 0.04 m s−1). Increasing the liquid flow rate significantly (uL = 0.1 m s−1) smooths liquid distribution, reducing the maldistribution factor by half. Gas velocity also helps phase uniformity but to a smaller extent. It is estimated that even higher fluid velocities (at least tripled) would be required to feed all channels equally. Adding stack of distribution plates of variable cell density at the top of the monolith does not enhance the quality of the liquid distribution, except at low liquid velocity

Maîtrise de l'acidité des vins (désacification par précipitation de malates de calcium et simulation des équilibres physico-chimiques à l'aide du logiciel Mextar)

TOULOUSE-ENSIACET (315552325) / SudocSudocFranceF

Microfiltration tangentielle appliquée à l'oenologie (compréhension et maîtrise des phénomènes de colmatage)

La clarification des vins par procédés membranaires en particulier la microfiltration tangentielle a toujours été limitée par le colmatage, générant des flux de perméation faibles incompatibles avec la rentabilité économique. La compréhension, la maîtrise, ainsi que l'anticipation des phénomènes de colmatage font l'objet de ce travail. Dans un premier temps, la contribution individuelle puis en mélange des composés du vin (tannins, pectines, mannoprotéines et levures) au colmatage d'une membrane céramique multicanaux a été évaluée. Une approche fondamentale a permis de proposer des mécanismes de colmatage : la présence des pectines induit les flux de perméation les plus faibles en formant un gel à la surface de la membrane tandis que les levures semblent au contraire avoir un effet protecteur dans le cas d'un vin brut. Parce qu'il représente le flux au-delà duquel un colmatage irréversible apparaît à la surface de la membrane, le flux critique pour l'irréversibilité est un paramètre clef pour contrôler le colmatage. Dans le cas de la filtration de vin, aucun flux critique n'a pu être déterminé ce qui a conduit à définir un critère identifiant une zone de travail où le degré de colmatage reste acceptable. La dernière partie de cette thèse est consacrée à l'étude de la filtration dynamique (RVF) pour une éventuelle application dans le secteur vinicole. Cette technique est testée en présence de deux membranes organiques différentes: PES (hydrophile) et PTFE (hydrophobe). Les observations ont permis de mettre en évidence l'efficacité du système contre le colmatage des membranes PES induite par l'action de l'agitateur. Le colmatage des membranes PTFE est énormément affecté par les interactions molécules/membrane rendant la filtration dynamique inefficace pour lutter contre le colmatage de ces membranes.Wine clarification by membrane processes mainly cross-flow microfiltration has been limited by membrane fouling generating low permeate fluxes with economic efficiency. Understanding, controlling and anticipation of fouling are the main goals of this work. In a first time, the individual contribution of wine compounds (tannins, pectins, mannoproteins and yeasts) to a multichannel ceramic membrane fouling was evaluated. The fouling mechanisms were analyzed using a fundamental approach. The presence of pectins induce the lowest fluxes by a gel-type formation at the membrane surface while yeasts presence tends to reduce fouling in the case of crude wine (case of mixed components). Because it represents the flux beyond which irreversible fouling appears on the membrane surface, the critical flux for irreversibility is a key parameter to control fouling. No critical flux for irreversibility could be measured, hence a criterion that identifies a range of operating conditions where the degree of fouling remains acceptable was proposed. The last part of this work was devoted to the study of dynamic filtration (RVF) for further application in wine sector. This technique was tested with two different membranes: hydrophilic PES and hydrophobic PTFE. Results have allowed to demonstrate the efficiency of the system to reduce fouling in the case of PES membrane. Fouling of PTFE membrane is greatly influenced by molecules / membrane interaction making dynamic filtration ineffective in reducing of membrane fouling.TOULOUSE-INP (315552154) / SudocSudocFranceF

The protective role of dissolved carbon dioxide against wine oxidation: a simple and rational approach

Aims: During wine making, oxygen and carbon dioxide are often simultaneously present in the liquid phase. We propose a simple rational approach, based on usual chemical engineering and thermodynamic principles, to provide understanding and practical rules for controlling the effects of these two dissolved gases, and especially their inter-relationship. Furthermore, this study proposes an explanation for the “protective” effect against oxidation, which is reported when high concentrations of carbon dioxide are present in musts and wines. Methods and results: The theoretical quantitative relation, termed “binary gas equilibrium line”, between the maximum possible concentration of dissolved oxygen in respect to dissolved carbon dioxide was derived and, in our experiments, corresponded to CO2max ≅ -0,005 CCO2 + 7,9 mg.L-1. Specific saturation experiments using simultaneous injection of air and gaseous carbon dioxide were performed and the experimental results allowed us to validate this theory in the case of gas bubbling in a liquid. Conclusion: It is shown that complete protection is only obtained when carbon dioxide is generated by the fermentation in the liquid. An interesting parallel conclusion is that micro-oxygenation is totally inefficient in such periods. In the case where there is no production of CO2 but where a high initial dissolved carbon dioxide concentration is present, the “protective” effect acts only by reducing the rate of oxygen transfer. Significance and impact of the study: The physical understanding of this phenomenon can be found in the fact that as soon as a gaseous air or pure oxygen phase is in contact with a carbon dioxide saturated liquid, the dissolved carbon dioxide, which is not at equilibrium with the gaseous phase, tends to escape into this gaseous phase. This study points out the complexity of the gas-liquid equilibrium when two dissolved gases are simultaneously present in a liquid and its implication in the winemaking process

Prediction and mastering of wine acidity and tartaric precipitations: the Mextar&reg; software tool

The MEXTAR® software is a mathematical tool able to predict the physicochemical state of a wine. Solving rigorously physicochemical equilibria, including complexation ones, it enables to simulate various operations endured by a wine: tartaric precipitations, acid addition, acid removal, malolactic fermentation. Using only classical chemical analytic determinations, namely, pH, total acidity, tartaric acid and potassium content, MEXTAR® computes the physicochemical state of a wine before and after the endured operation: pH and total acidity, tartaric salts supersaturation and the associated saturation temperature taking into account both the ionic activity coefficients and the complexed fraction of the involved ions, amount of tartaric salts that can be precipitated to obtain either a supersaturation chosen by the user at a given temperature or a chosen final saturation temperature, required amount of acidification or desacification chemical substances to reach a chosen pH or total acidity. The article describes the theoretical background upon which MEXTAR® has been developed and details the computation procedures associated to the simulation of the operations described above. Iterative processes are used to determine the various parameters enounced above. They aim in particular at the verification of the electroneutrality of the sample. However, at first electroneutrality is rarely verified because the wine chemical analytical determination is never exhaustive. Therefore, we introduce the concept of «vinic acid» to compensate the negative ion deficit of usual wine chemical analytical determination. This «vinic acid» is describe as a diacid with a fixed second dissociation constant (pK2 = 5) and a first dissociation constant determined automatically by MEXTAR®. This enables MEXTAR® to simulate accurately experimental tartaric precipitations for several samples. Thanks to the predicting capacity of MEXTAR®, the correlation between the total polyphenol content (IPT) in red wines and the difficulty to stabilise high IPT wine with respect to tartaric salts is confirmed. Finally, malolactic fermentations are also well simulated. A validation of MEXTAR® for the acid addition or removal has yet to be done when reliable experimental data are available