Institut für Chemie und Bioanalytik
Dauerhafte URI für die Sammlunghttps://irf.fhnw.ch/handle/11654/24
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Publikation Continuous in situ lactic acid extraction from sweet whey fermentation broth using a tubular membrane contactor(2022) Demmelmayer, Paul; Pérez, Alan; Riedl, Wolfgang; Kienberger, MarleneBackground Whey, as the major dairy by-product, has become a severe problem for the dairy industry because its demand has decreased, while its production has increased in the past years. Since the high demand for dairy products tends to further increase, suitable routes for whey valorization are required. Whey contains valuables like lactate, but due its composition matrix, processing is challenging. The high sugar content in whey makes it a potential feedstock to produce lactic acid (LA) via microbial fermentation. Still, the known drawbacks of biotechnological LA production, such as growth inhibition by the product, the use of neutralizers, low productivity, and high overall costs of the process must be overcome. In situ LA recovering using a suitable separation technology is a potential strategy to overcome the mentioned drawbacks. In this work, the in situ LA extraction from a whey fermentation broth was evaluated. Sweet whey was used as feedstock for lactic acid production via microbial fermentation, while LA was recovered by reactive liquid-liquid extraction using a tubular membrane contactor. Method The feed material used in this work is a fermentation broth from sweet whey, which was filtered prior to extraction experiments using microfiltration. In a first series of experiments, two-phase extraction experiments were conducted in temperature controlled separation funnels, to investigate different solvent phase combinations for the lactic acid extraction. Special attention was paid to replace commonly applied fossil-based solvents with green alternatives, such as deep eutectic solvents (DES). After extraction, the extract was treated in a back-extraction step to recover LA from the solvent phase. Here, an anti-solvent, e.g. heptane or p-cymene, was used to transfer LA to the receiving phase, which was water. Afterwards the performance of reactive liquid-liquid extraction of LA using a PTFE membrane contactor was evaluated by using two potential solvent phases, namely tri-n-octyl amine (TOA) with n-decanol and a DES formed from thymol and menthol. From the experimental results the overall mass transfer coefficient was calculated based on a rigorous mass transfer model to predict the LA concentration in both phases. Finally, performance of the in situ LA recovery from sweet whey by using membrane contactor was investigated from both, experimentally and theoretically points of view. Results & Conclusion In the two-phase extraction experiments, the reactive extractants Aliquat336, TOA, trioctylphosphinoxid (TOPO), and the mixture Aliquat336/TOA were found to be most efficient with the diluents 1-decanol, limonene, and a deep eutectic solvent consisting of thymol and menthol. Especially, the DES and limonene are promising as they can be produced from renewable resources. With respect to back-extraction, heptane and p-cymene showed the highest efficiencies for transferring lactic acid into the receiving phase water. In the next step, the selected solvents were used to perform LA recovery in the tubular membrane contactor from a model aqueous solution of LA and a fermentation broth of sweet whey. The proposed technology for valorizing dairy waste through LA biotechnological production shows the feasibility to scaling it up.06 - PräsentationPublikation Liquid–liquid equilibrium and molecular toxicity of active and inert diluents of the organic mixture tri-iso-octylamine/dodecanol/dodecane as a potential liquid membrane for lactic acid removal(American Chemical Society, 2019) Pérez, Alan; Gómez, Verónica M.; Rodríguez-Barona, Sneyder; Fontalvo, JavierLactic acid can be in situ removed from a fermentation broth through reactive liquid extraction or a liquid membrane to enhance the fermentation process. The organic mixture tri-iso-octylamine (TiOA)/dodecanol/dodecane at 10 vol % of the amine is a potential organic mixture for lactic acid removal. Liquid–liquid equilibria with lactic acid aqueous solutions and molecular toxicity on the bacteria Lactobacillus casei ATCC 393 were measured with several dodecanol proportions in dodecane (0 to 90 vol %) and 10 vol % TiOA as potential solvents or membrane phases for LA removal from a fermentation broth. Effects of the organic phase on the bacteria as cell growth, biomass production, glucose consumption, productivity, and product to biomass yield are analyzed. Dodecanol increases the lactic acid chemical equilibrium constant for the liquid–liquid equilibria, while increasing the molecular toxicity on the bacteria. However, for dodecanol concentrations from 30 to 40 vol % the value of the chemical equilibrium constant is high enough for lactic acid distribution between the phases and its toxicity is low enough on the bacteria, making a proper range of dodecanol concentrations for lactic acid removal. Also, the distribution coefficient and the chemical equilibrium constant are fitted as a function of the dodecanol concentration in the organic mixture.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Liquid–liquid equilibria for trioctylamine/1-dodecanol/citric acid/water system at 303.1 and 308.1 K: Experimental data and prediction(American Chemical Society, 2020) Murcia-Montalvo, Laura; Pérez, Alan; Fontalvo, JavierThe present work experimentally tests the liquid–liquid equilibria (LLE) of aqueous citric acid (CA) solutions with trioctylamine (TOA) in 1-dodecanol at 303.2 and 308.2 K. A predictive model has been developed based on the experimental data. This model considers the physical dissolution of CA and complexation with TOA. At low CA concentrations, the stoichiometric ratio of acid/amine is (1:1). However, the acid/amine ratios of (1:1), (1:2), and (2:1) are present at high CA concentrations. The equilibrium constants for the different complexes were determined and compared to previous studies, which employed other organic solvents. The equilibrium constants obtained in this study are comparatively higher, making 1-dodecanol an attractive solvation medium. Also, the literature presents LLE experiments with contact times from minutes to hours. Because of this lack of consensus, this work displays experimental evidence to suggest contact and settling times required for experimental evaluation of the equilibria in liquid–liquid systems based on the standard deviation.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Liquid–Liquid equilibria for trioctylamine/1-dodecanol/lactic acid/water system at 306.1, 310.1 and 316.1 K: Experimental Data and Prediction(American Chemical Society, 2016) Pérez, Alan; Rodríguez-Barona, Sneyder; Fontalvo, JavierLiquid–liquid equilibria of aqueous solutions of lactic acid with trioctylamine diluted in 1-dodecanol was measured experimentally at three temperatures (306.1, 310.1, and 316.1 ± 0.1 K). During the transfer process, lactic acid reacts with trioctylamine to produce an amine–lactate complex. Two models were proposed to predict the liquid–liquid equilibria. The first model considered the equilibrium constant of chemical reaction and the distribution coefficient. Those parameters have been determined by fitting the experimental data. The distribution coefficients have also been experimentally measured. It was found that as temperature increases, the distribution coefficient increases and equilibrium constant decreases. The second proposed model involved the non-random two liquid activity model. Energies of binary interaction and the equilibrium constant of chemical reaction were fitted to experimental data. The equilibrium constant and partition coefficients show the same trends as the first model; however, the first model shows a better prediction as compared to the second model of the liquid–liquid equilibrium data. These two models are especially suitable at low lactic acid concentrations in the aqueous phase where the experimental standard deviation is low.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Liquid–liquid equilibria of lactic acid/water solutions in tri-iso-octylamine/dodecane/1-dodecanol at 306.1, 310.1, and 316.1 K. Experimental data and prediction(American Chemical Society, 2019) Pérez, Alan; Rodríguez-Barona, Sneyder; Fontalvo, JavierThe liquid–liquid equilibria of systems that involves lactic acid in the aqueous phase and tri-iso-octylamine with diluents as dodecane and 1-dodecanol (active or/and inert) were measured experimentally at three temperatures (306.15, 310.15, and 316.15 K). A previous liquid–liquid equilibrium model that is based on Nernst’s distribution law and mass action law equilibrium equations was extended and generalized for stoichiometric ratios (amine/acid) 1:n. The effect of the diluents and the tertiary amine on the liquid–liquid equilibrium is shown and quantified in terms of the predicted values of the distribution coefficient, chemical equilibrium constants, and temperature. The lactic acid concentration in equilibrium for the organic phase decreases as follows: water/LA/TiOA/1-dodecanol system > water/LA/TiOA/dodecane/1-dodecanol > system water/LA/TiOA/dodecane system.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Emerging Strategies for Ethanol Purification(Apple Academic Press, 2022) Pérez, Alan; Quintero, Javier; León, Juan A.; Hernández Almanza, Ayerim Y.; Balagurusamy, Nagamani; Ruiz Leza, Héctor; Aguilar, Cristóbal N.04A - Beitrag SammelbandPublikation Influence of pulping conditions on the pulp yield and fiber properties for pulping of spruce chips by deep eutectic solvent(Springer, 2023) Pérez, Alan; Roy, Yagnaseni; Rip, Constantijn; Kersten, Sascha R. A.; Schuur, BoeloThe chemical pulping of wood chips using deep eutectic solvents (DES-pulping) has emerged as an alternative technology to conventional pulping in the paper industry, allowing the production of pulp in combination with the recovery of lignin and sugars for valorization. A challenge in the development of this technology is the understanding of how the operating conditions influence the crucial pulp manufacturing parameters such as delignification percentage, pulp yield, and fiber quality. This work is focused on investigating the effect of operating conditions such as cooking temperature, cooking time, liquor-to-wood ratio, initial water content on DES, type of mixing, the addition of a pre-treatment step (pre-impregnation of DES into the wood chips) to cooking process, and DES composition (lactic acid:choline chloride, lactic acid:sodium chloride, and lactic acid:sodium bromide) on the cooking of wood chips by DES. A shortcut quality evaluation parameter (Q), defined as the product of the fiber length and the degree of delignification quantified the quality of the pulping process in a single value, shows values similar to a reference unbleached kraft pulp for cooking at 130 °C in a range of cooking times from 3 to 4.5 h at a L/W of 10:1 by using lactic acid:choline chloride DES. More elaborate property analysis on the fibers showed that several of the the quality-indicating properties of the fibers (coarseness, shape factor, fibril area, and crill index) are comparable with typical sulfite pulping fibers.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Integration of a liquid membrane in Taylor flow regime with a fermentation by Lactobacillus casei ATCC 393 for in-situ lactic acid removal(Elsevier, 06/2019) Pérez, Alan; Rodríguez-Barona, Sneyder; Fontalvo, JavierA new type of liquid membranes called liquid membrane in Taylor flow was integrated to a lactic acid fermentation, using Lactobacillus casei ATCC 393, for lactic acid removal during fermentation. The performance in terms of lactic acid production of the hybrid batch system is compared to a conventional batch fermentation. Lactic acid removal rate increases proportionally with the LA concentration within the fermenter. The lactic acid, the biomass production and the LA productivity in the hybrid system increased by 41.8, 12 and 26.6%, respectively, as compared to the conventional batch fermentation. However, toxicity effects reduce LA to glucose yield in 15.9% as compared to conventional fermentation. Liquid membranes in Taylor flow results promising for enhancing batch and continuous fermentation processes by a hybrid system.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Study of overall mass transfer coefficients in a liquid membrane in Taylor flow regime: Calculation and correlation(Elsevier, 12/2018) Pérez, Alan; Van der Bruggen, Bart; Fontalvo, JavierThe use of a liquid membrane in Taylor flow regime is a recent technology, which extends and generalizes the definition of a membrane. It has been developed and tested for lactic acid removal. A challenge in understanding the technology is that the values of the overall volumetric mass transfer coefficients are not known, and it is unclear how they are related with the operational conditions. In this work, the overall volumetric mass transfer for the liquid membrane in Taylor flow was calculated from experimental results and three empirical models, two of which are from literature and one was developed in this work based on dimensional analysis. From combination of experimental results and the developed models the main variables (operational conditions) of the liquid membrane in Taylor flow that have a strong influence on the overall volumetric mass transfer coefficients (in the donor and in the membrane phase) were defined. The relative velocity results as the variable that has the largest influence on the performance of this new liquid membrane technology.01A - Beitrag in wissenschaftlicher ZeitschriftPublikation Liquid extraction with immobilized liquids for product recovery from fermentation broths(Elsevier, 2022) Pérez, Alan; Gössi, Angelo; Riedl, Wolfgang; Schuur, Boelo; Fontalvo, Javier; Thatoi, Hrudayanath; Mohapatra, Sonali; Das, Swagat KumarNowadays, many fermentation chemicals are produced at an industrial scale. Numerous technological improvements have been developed and implemented to achieve high quality and quantity of fermentation products. However, several drawbacks in fermentation processes still limit their application at an industrial level. In situ product removal (ISPR) is a potential alternative to overcome the conventional drawbacks of the fermentative processes, increasing the fermentation's productivity and reducing the separation steps for recovery and purification. Currently, liquid extraction has emerged as a promising separation technology for ISPR, with immobilized liquids such as membrane-assisted extraction and microchannel liquid membrane, due to the high mass transfer rates, scalability, easy integration, and efficiency. This chapter will discuss these technologies regarding their integration into fermentative processes.04A - Beitrag Sammelband