Fish Oil Valorization using Supercritical Carbon Dioxide

Trabajo presentado en: 17th European Meeting on Supercritical Fluids. 2019, 8-11 de abril, Ciudad RealMINECO(CTQ2012-39131-C02-01), JCyL(BU301P18) and ERDF I also owe my gratitude to MINECOfor financing my predoctoral contract (BES-2013-063937

Extraction of Marine Collagen Derivatives from Hoplostethus mediterraneus Cuvier, 1829 Using a Pressurized Water - CO2 System

Trabajo presentado en: 19th European meeting on Supercritical Fluids (EMSF 2023), organized by the International Society for the Advancement of Supercritical Fluids, Budapest, 21-24 may, 2023The study indicated a new approach for producing nutritional and functional biomaterial from a relatively unutilized marine source while contributing to environmentally responsible and sustainable practices of efficient resource use.This work was supported by TUBITAK 2219 (Post-doc international scholarships programme) and the Agencia Estatal de Investigación (Spain) [grant numbers PID2019–104950RB-I00, TED2021-129311B-I00 and PDC2022-133443-I00] and the Junta de Castilla y León (JCyL) and the European Regional Development Fund (ERDF) [grant number BU050P20]. RM is supported by a Beatriz Galindo Research Fellowship [BG20/00182]

High-pressure phase equilibria of the pseudo-ternary system carbon dioxide + ethanol + fish oil

Ponencia presentada en: 16th European Meeting on Supercritical Fluids, 25 a 28 de abril de 2017, LisboaThis work provides experimental phase equilibrium data of the pseudo-ternary system CO2 + ethanol + fish oil, a system of interest in pharmaceutical and food-industry applications such as the enzymatic production of fatty acid ethyl esters at mild, non-oxidative conditions. Measurements were carried out in a high-pressure variable-volume view cell in the temperature range 323.15-343.15 K and at pressures from 10 to 30 MPa. The Peng-Robinson equation of state was used to satisfactorily correlate experimental data.European Regional Development Fund (ERDF), Spanish Government (MINECO) and Junta de Castilla y León for financial support (projects CTQ2012-39131-C02-01 and BU055U16). RM acknowledges MINECO (BES-2013-063937

Phase behaviour of the pseudo-ternary system carbon dioxide + ethanol + fish oil at high pressures

This work provides experimental fluid phase equilibrium data of the pseudo-ternary mixture CO2 + ethanol + fish oil, a system of interest in pharmaceutical and food-industry applications such as the production of omega-3-enriched lipid derivatives at mild, non-oxidative conditions. Experimental tie-lines were obtained by means of an analytical isothermal method with recirculation of the vapour phase. Measurements were carried out in the temperature range 323.15 K–343.15 K and at pressures from 10 MPa to 30 MPa. The Peng-Robinson equation of state coupled with the conventional van der Waals mixing rules with two adjustable parameters was used for experimental data correlation.Spanish Government through MINECO and Junta de Castilla y León for financial support of the projects CTQ2012-39131-C02-01 and BU055U16, respectively, 16 both co-financed by the European Regional Development Fund (ERDF

High pressure CO2 solubility in food model solutions and fruit juices

Measurements of CO2 solubility were performed in different media, pure water, model citrate buffer solutions at different pH values and in the presence of different sugar content and in real apple and carrot juices. Solubility was determined in the pressure range from 8 to 20 MPa and in the temperature range from 308 to 318 K. CO2 solubility in citrate buffer solutions at pH = 3.8 and pH = 6.2 was slightly lower than CO2 solubility in pure water. A Chrastil-type equation according to Fornari’s approach was used to fit CO2 solubility data in pure water and model solutions. A new term was introduced in this equation to account for the decrease in solubility of CO2 in the presence of sugar in the liquid media.Spanish Government (MINECO) and the European Regional Development Fund (ERDF) for financial support of project CTQ2015-64396-

Supercritical carbon dioxide extraction of quinoa oil: Study of the influence of process parameters on the extraction yield and oil quality

The supercritical CO2 extraction of oil from four different quinoa varieties has been studied in this work. For this purpose, the influence of extraction temperature (40–60 °C), pressure (20–40 MPa) and raw material size (250–1000 μm) on the extraction rate has been considered. The extraction rate resulted to be faster the higher the pressure whereas the temperature had less influence on the extraction kinetics. The experimental data were modelled using the Sovova’s kinetic model. The quality of the oil extracted has been evaluated in terms of antioxidant activity (AA), fatty acid profile and tocopherol content. The highest AA was obtained for quinoa oil extracted at 40 MPa and 40 °C; this oil presented high content of polyunsaturated fatty acids (63% of the total) and significant amount of tocopherols (2.5 mg/g oil). Quinoa oil extracted using CO2 presented higher antioxidant capacity and tocopherol content than quinoa oil extracted with hexane, regardless the quinoa variety used.Junta de Castilla y León and the European Regional Development Fund (ERDF - FEDER) for the financial support of project BU055U1

Modification of brewer’s spent grain after sc-CO2 extraction: improvement of sugar and phenolic compounds release

Póster presentado en: EIFS2022, the 2nd Iberian Meeting on Supercritical Fluids (2º Encontro Ibérico de Fluidos Supercríticos / 2º Encuentro Ibérico de Fluidos Supercríticos), to be held on 28.February - 2.March 2022 in Coimbra, Portugal.Brewer ́s spent grain (BSG) is the solid by-product generated in breweries after the mashing and wort filtration process. It comprises about 85 % of the total by-products, generating approximately 20 kg per 100 L [1]. BSG presents a valuable chemical composition with a high content of protein and carbohydrates, 5 % of lipids and an important source of phenolic compounds. Among the different techniques proposed to valorize BSG, supercritical CO2 (sc-CO2) has become a promising technology to process biomass. The main aim of this work was to assess the effect of sc-CO2, after BSG oil extraction, on the subsequent enzymatic hydrolysis to hydrolyze the polysaccharide fraction into monomeric sugars by comparing the sugar yields of sc-CO2 and non-scCO2 treated BSG. After sc-CO2 treatment at 40 MPa and 80 oC, the raffinate obtained was subjected to enzymatic hydrolysis by cellulase at different enzyme dose. At the sc-CO2 extraction the carbohydrate fraction remained in the raffinate phase after extraction. Glucose yield increased with enzyme concentration for non-treated and sc-CO2 treated BSG. Higher yields of glucose were obtained for sc-CO2 treated compared to non-treated sc-CO2 for all the enzymes concentrations. The percentage increase in glucose yield for sc-CO2 treated and non-treated BSG was 8, 14 and 18 % for the three cellulase concentrations essayed in this work, 0.25, 0.5 and 1 %, respectively. The hydrolysis kinetics for xylose and arabinose have been also determined for non-treated and sc-CO2 treated BSG at 1 % of cellulase dose. Although not big differences were observed in the final sugar yield in the hydrolysates, the initial hydrolysis rate were significant higher for the sc-CO2 treated BSG than for the untreated samples. The higher enzymatic hydrolysis rate and yield obtained in the raffinate-BSG after sc- CO2 treatment compared with non-treated BSG could be attributed partially to the removal of the lipid fraction. As it has been described in literature [2], fats and oils could influence the susceptibility of carbohydrates to enzymes. This improvement was also due to surface morphology modification. The structural and chemical changes of untreated and sc-CO2 treated BSG was assessed by scanning electron microscopy and X-ray powder diffraction (XRD). Although the XRD pattern after sc-CO2 treatment indicated that the pre-treatment was not strong enough to modify the BSG crystallinity, the raffinate exhibited an irregular porosity and lamellar structure. sc-CO2 broke partially some structural barriers allowing a better enzyme access. Furthermore, some phenolic compounds were determined in the enzymatic hydrolysates at the end of the hydrolysis by using 1 % of cellulase (Table 1). It was observed that for p-coumaric acid and ferulic acid, a concentration 31 and 24 % higher, respectively, was obtained in the BSG hydrolysates after sc-CO2 treatment, while for vanillin similar concentration was obtained in both hydrolysates. The concentration of p-coumaric acid and vanillin after cellulase hydrolysis was lower than the values previously reported for the same BSG by alkaline, xylanase (1%) and subcritical water hydrolysis [3], [4]. Nevertheless, for ferulic acid, only a higher value was reached for alkaline hydrolysis.JCyL and ERDF for financial support of project BU050P20 Agencia Estatal de Investigación for financial support of project PID2019-104950RB-I00 / AEI / 10.13039/501100011033 JCyL and ESF for E. Trigueros (ORDEN EDU/574/2018) and P. Alonso-Riaño predoctoral (EDU/556/2019) contracts R. Melgosa is supported by a Beatriz Galindo Research Fellowship [BG20/00182

High pressure carbon dioxide technology: application to orange juice

Ponencia presentada en: 16th European Meeting on Supercritical Fluids, 25 a 28 de abril de 2017, LisboaHigh pressure carbon dioxide (HPCD) treatment has been applied to orange juice as alternative non-thermal treatment. Kinetics inactivation for pectin methyl esterase has been determined at different operating conditions. PME residual activity was correlated succesfully to the two-fraction model. Some quality parameters such as colour, pH, calcium content, turbidity and particle size distribution (PSD) were also determined right after HPCD treatment. PSD shows that HPCD treatment results in a homogenization effect with a volume increase of small particles and a volume decrease of large particles regarding the non-treated orange juice.MINECO (CTQ2015-64396-R). R. Melgosa acknowledges MINECO for a grant (BES-2013-063937).Spanish Government through MINECO (CTQ2015-64396-R). R. Melgosa acknowledges MINECO for a grant (BES-2013-063937

Glicerolisis de aceite de sardina catalizada por una lipasa dependiente de agua en diferentes tert-alcoholes como medio de reacción

The production of monoacylglycerol rich in polyunsaturated fatty acids (PUFA) via enzymatic glycerolysis of sardine oil in a homogeneous system was evaluated. Reactions were conducted in two different tert-alcohols. Based on the phase equilibrium data, the amount of solvent added to create a homogeneous system has been calculated and optimized. The immobilized lipase used in this work was Lipozyme RM IM from Rhizomucor miehei, a water dependent lipase. The amount of water added as well as other reaction parameters were studied to evaluate the optimum conditions for monoacylglycerol obtencion. An initial reactant mole ratio glycerol to sardine oil 3:1, 12 wt% of water based on glycerol content and 10 wt% of lipase loading (based on weight of reactants), achieved a MAG yield of around 70%, with nearly 28 wt% PUFA, with low free fatty acid content (lower than 18 wt%).En este trabajo se ha estudiado la producción de monoacilglicéridos, ricos en ácidos grasos poliinsaturados (AGPI), mediante glicerolisis enzimática de aceite de sardina. La reacción se ha llevado a cabo en dos tert-alcoholes para conseguir de esta forma un medio homogéneo de reacción. La cantidad de disolvente añadida al medio de reacción se ha optimizado y calculado en base al equilibrio de fases de los componentes del sistema. La lipasa empleada como biocatalizador ha sido la enzima inmovilizada Lipozyme RM IM de Rhizomucor miehei, una lipasa dependiente de agua. Se ha estudiado el efecto de distintos parámetros cinéticos, así como de la cantidad de agua añadida al medio de reacción, en la producción de monoacilglicéridos. De los resultados obtenidos, se puede concluir que, para una relación molar inicial de reactantes glicerol:aceite de sardina de 3:1, un 12 % en peso de agua en base al glicerol y un 10 % en peso de lipasa, en base al peso de reactantes; se puede llegar a conseguir un rendimiento en monoacilglicéridos alrededor del 70 % en peso, con casi un 28 % en peso de AGPI y un bajo contenido en ácidos grasos libres (menor del 18 % en peso).Spanish Government through MINECO and the European Regional Development Fund (ERDF) for financial support to the project CTQ2012-39131-C02-01. They wish to thank Novozymes A/S for kindly supplying the enzymes. RM acknowledges MINECO for an FPI grant (reference BES-2013-063937)

Liquid–liquid equilibrium for ethanolysis systems of fish oil

Enzymatic alcoholysis of fish oil can produce monoacylglycerols rich in polyunsaturated fatty acids at atmospheric pressure and low temperature. Biocatalysis in organic solvents helps to create a homogeneous reaction system for the reactants, ethanol and fish oil. This work presents liquid–liquid equilibrium at two different temperatures (303.2 K and 323.2 K) and at atmospheric pressure for two solvent-systems in the ethanolysis of fish oil: ethanol + oil + tert-pentanol and ethanol + oil + hexane. Experimental solubility (binodal) curves were obtained by the cloud point method and tie-line composition was obtained by density and high-temperature gas chromatography. The consistency of experimental tie-line data was checked by using the Othmer–Tobias equation. The experimental liquid–liquid data were correlated satisfactorily by the nonrandom two liquid model for activity coefficient calculations.MINECO (CTQ2012-39131-C02-01) and CDTI (ref. IDI-20111225