Soybean Oil Deodorizer Distillate Research Articles

Batch and continuous γ-alumina-catalyzed FAME production from soybean oil deodorizer distillate by interesterification

This paper presents data for a batch and continuous fatty acid methyl esters (FAME) production through heterogeneous catalysis interesterification with methyl acetate, using soybean oil deodorizer distillate (SODD) as feedstock, a high-acid by-product of problematical destination, generated during the soybean oil refining process. As a reaction catalyst, γ-alumina with high catalytic activity, acid character, and an interesting specific area was synthesized and used in the processes. The SODD presented a significant FFA content of 35.2 ± 0.4 wt% and low convertibility in esters (48.0 ± 0.9 %) pointing to high impurity content. By statistical design, the parameters optimization (temperature, methyl acetate:SODD mass ratio, and catalyst load) of the batch reactor returned results that indicated the reliability and reproducibility of the proposed model, allowing predicting the system behavior at autogenous pressure, where around 80.0 wt% of ester yield and 5.4 wt% of triacetin (TA) yield was obtained after 2 h. By kinetics analysis, a FAME yield higher of 90 wt% and TA yield of 13.90 wt% were achieved after 4 h. From these results, continuous production of FAME and TA could be evaluated, where the results obtained permitted to affirm that the acid heterogeneous interesterification can be an interesting process to biodiesel synthesis from SODD.

Non-isothermal (trans)esterification of linoleic acid and soybean oil deodorizer distillate with methanol under subcritical conditions

Soybean oil deodorizer distillates (SODD), a by-product of soybean oil refining, primarily comprised of free fatty acids (FFA, 40.62–51.23 wt%), acyglycerides (22–25 wt%), and unsaponifiable matter (19.81–42.23 wt%), was explored as a potential feedstock for the synthesis of fatty acid methyl ester under subcritical conditions. Oil mixtures of linoleic acid and soybean oil were used as models to investigate the effects of reactor loading (RL = 25, 50, 90%), solvent-to-fatty acid ratio (SFR = 0.15–1.5 mL/g), mixing (0, 300 rpm), temperature (30–245 °C), and reaction time under non-isothermal and isothermal conditions. In addition, water and acetic acid were used as additives to investigate their effect on the reaction. Under favorable reaction conditions of 90% RL, SFR of 0.5 mL/g, and reacted non-isothermally to 245 °C and held for 100 min with stirring, high conversions or yields (87–89%) could be achieved when using SODDs having different total fatty acid content (59.37–77.42 wt%). The effect of unsaponifiable matter in significant quantities and some simple strategies to overcome possible limitations in the use of such feedstock were also looked into. The presence of high FFA allows (trans)esterification to be carried out under subcritical conditions without the need of adding a catalyst.

Enzymatic Synthesis of Fatty Acid Isoamyl Monoesters from Soybean Oil Deodorizer Distillate: A Renewable and Ecofriendly Base Stock for Lubricant Industries.

In this study, soybean oil deodorizer distillate (SODD), a mixture of free fatty acids and acylglycerides, and isoamyl alcohol were evaluated as substrates in the synthesis of fatty acid isoamyl monoesters catalyzed by Eversa (a liquid formulation of Thermomyces lanuginosus lipase). SODD and the products were characterized by the chemical and physical properties of lubricant base stocks. The optimal conditions to produce isoamyl fatty acid esters were determined by response surface methodology (RSM) using rotational central composite design (RCCD, 23 factorial + 6 axial points + 5 replications at the central point); they were 1 mol of fatty acids (based on the SODD saponifiable index) to 2.5 mol isoamyl alcohol, 45 °C, and 6 wt.% enzymes (enzyme mass/SODD mass). The effect of the water content of the reactional medium was also studied, with two conditions of molecular sieve ratio (molecular sieve mass/SODD mass) selected as 39 wt.% (almost anhydrous reaction medium) and 9 wt.%. Ester yields of around 50 wt.% and 70 wt.% were reached after 50 h reaction, respectively. The reaction products containing 43.7 wt.% and 55.2 wt.% FAIE exhibited viscosity indices of 175 and 163.8, pour points of −6 °C and −9 °C, flash points of 178 and 104 °C, and low oxidative stability, respectively. Their properties (mainly very high viscosity indices) make them suitable to be used as base stocks in lubricant formulation industries.

Continuous production of fatty acid methyl esters from soybean oil deodorized distillate and methyl acetate at supercritical conditions

This work aimed to investigate the continuous production of fatty acid methyl esters (FAME) from soybean oil deodorizer distillate (SODD) and methyl acetate (MA) under supercritical conditions. The influence of temperature (275–300–325 °C), MA:SODD mass ratio (0.5:1–1:1–2:1) and residence time (7.5–10–20–30–40 min) were analyzed in the FAME and triacetin (TA) production. Thermal decomposition phenomenon of esters at high temperatures and mass transfer were verified. Residence time of 10 min showed promised results in all experimental conditions. The most suitable condition was 300 °C, MA:SODD molar ratio of 1:1 and residence time of 10 min, which allowed to obtain a 87.7% FAME yield. A 38,51% thermal decomposition was observed at 325 °C and 0.5:1 MA:SODD mass ratio in 40 min. Thus, SODD with methyl acetate showed to be efficient, enabling the occurrence of acid transesterification and interesterification reactions.

A novel method based on saponification coupled to micelle-extraction for recovering valuable bioactive compounds from soybean oil deodorizer distillate

The feasibility of using saponification coupled to extraction with mixed micellar systems to recover bioactive compounds from soybean oil deodorizer distillate, was evaluated for the first time. Under the selected conditions, saponification with KOH 0.6 M and aqueous micellar system prepared with Tergitol 15-S-7 9% w/w, rhamnolipids 0.25 %w/w and sodium citrate 100 mM pH 5.00, at 65 °C, allow the recovery of almost 100% of α- and δ- tocopherols, and 90% of γ-tocopherols. LC-MS measurements demonstrated that the final extract also contained phytosterols and squalene. Additionally, the obtained extract preserved about 100% of the total antioxidant activity. This result was attributable to the fact that 93% of the tocopherols recovered in the micellar phases resulted to be associated with surfactant micelles, environment that is known to improve their antioxidant capacity. These results open perspectives to the use of this methodology to extract these valuable compounds from complex oily sources.

Industrially concentrated tocopherols from soybean oil deodorizer distillate

Although the tocopherol concentration in Soybean Oil Deodorizer Distillate (SODD) regarding molecular distillation (MD) has been studied in the last 20 years, no scientific studies were published yet in international journals about the results of this technology when applied in an industrial scale. This research aimed to evaluate the tocopherols concentration through industrial patented MD technology in a vegetable oil refinery, using a phospholipase A2 enzymatic physical degumming process, packed dual temperature column deodorizer coupled to a double washer and a Tocoboost® patented technology. The results of the refinery production process from July 2019 to February 2020 could totalize over 81 days, comprising 243 samples and more than 1900 laboratory analysis. The input and output SODD samples were analysed by Gas Chromatography (GC), in which graphics of the automation system and mass balance of the refinery production ranges were also verified. The results showed that it is possible to achieve over five times Vitamin E concentration from non-modified soybean oil deodorizer distillate in a physic enzymatic phospholipase degumming process plant using a combination of advanced technology in order to separate high value-added molecules gained through studied hypotheses regarding vacuum, temperature, distiller models, backset flows, multiple stages of distillation, degradation and product recovery.

Performance of Liquid Eversa on Fatty Acid Ethyl Esters Production by Simultaneous Esterification/Transesterification of Low-to-High Acidity Feedstocks

Liquid Eversa was evaluated in hydrolysis of acylglycerols from soybean oil deodorizer distillate (SODD), as well as simultaneous esterification/transesterification of SODD with low-to-high free fatty acids (FFAs) content using ethanol as acyl acceptor. Hydrolysis of SODD at mild temperature (37 °C) and without pH control (water:SODD mass ratio of 4:1) increased its FFAs content from 17.2 wt.% to 72.5 wt.% after 48 h reaction. A cold saponification of SODD allowed a saponification phase (SODD-SP) to be recovered with 93 wt.% saponification index and 2.25 wt.% FFAs content, which was used to find the experimental conditions for simultaneous esterification/transesterification reactions by experimental design. Temperature of 35 °C, enzyme concentration of 8.36 wt.%, and molar ratio of 3.64:1 (ethanol:SODD-SP) were found as the best conditions for fatty acid ethyl esters (FAEEs) production from SODD-SP (86.56 wt.% ester yield after 23 h reaction). Under the same reaction conditions, crude SODD (17.2 wt.% FFAs) and hydrolyzed SODD (72.5 wt.% FFAs) yielded products containing around 80 wt.% FAEEs. Caustic treatment could increase the ester content to around 90 wt.% and reduce the FFAs content to less than 1 wt.%. Our results show the good performance of liquid Eversa in aqueous (hydrolysis reactions) and organic (esterification/transesterification reactions) media.

Solvent-free synthesis of partial glycerides and structured triglycerides from soybean oil deodorizer distillate: bottom-up approach

Solvent-free synthesis of partial glycerides and structured triglycerides from soybean oil deodorizer distillate: bottom-up approach

Integrated Utilization Strategy for Soybean Oil Deodorizer Distillate: Synergically Synthesizing Biodiesel and Recovering Bioactive Compounds by a Combined Enzymatic Process and Molecular Distillation.

Soybean oil deodorizer distillate (SODD) is well recognized as a good source of both biodiesel and high-value bioactive compounds of tocopherols, squalene, and phytosterols. To achieve a one-step synthesis of biodiesel and recovery of bioactive compounds from SODD, four commercial immobilized enzymes (Novozym 435, Lipozyme TLIM, Lipozyme RMIM, and Lipozyme RM) and one self-prepared immobilized lipase MAS1-H108A were compared. The results showed that immobilized lipase MAS1-H108A due to the better methanol tolerance and higher catalytic activity gave the highest biodiesel yield of 97.08% under the optimized conditions: molar ratio of 1:2 (oil/methanol), temperature of 35 °C, and enzyme loading of 35 U/g SODD, even after 10 persistent cycles without significant decrease of activity. Simultaneously, there was no loss of tocopherols and squalene in SODD during the enzymatic reaction. Pure biodiesel (characterized by fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR)) and a high concentration of bioactive compounds could be successfully separated by molecular distillation at 100 °C. In a word, this work provides an interesting idea to achieve environmentally friendly treatment of SODD by combining an enzymatic process and molecular distillation, and it is suitable for industrial production.

Influence of Industrial Processing on Physiochemical Characteristics of Soybean Oil and Deodorizer Distillates

The present study aimed to evaluate the impact of industrial processing (neutralization/degumming, bleaching, and deodorization) on physicochemical characteristics of soybean oil and soybean oil deodorizer distillate (SBO-DD) collected from two different industries. The substantial impact of processing was observed on all physicochemical parameters except the iodine value (IV) and saponification value (SV). Gas chromatography-flame ionization detector (GC-FID) and Gas chromatography-mass spectrometry (GC-MS) analytical techniques were used for the quantification of individual fatty acids, sterols, and 3-monochloropropane diol (3-MCPD) ester. Among the fatty acids, palmitic and linoleic acids were present at higher concentrations in all processing stages. Among sterols, β-sitosterol was found to be higher (25.65 and#181;g/g) in crude soybean oil and reduced to 16.44 and#181;g/g after processing till the final deodorization stage. 3-MCPD ester was developed during the neutralization/degumming process and further increased during bleaching and deodorization up to 315 and#181;g/kg, respectively. SBO-DD was found to be a rich source of total and individual sterols as compared to crude or processed soybean oil. High free fatty acid (FFA) level in deodorizer distillate indicated that SBO-DD is a potential source of biodiesel production.

Influence of Industrial Processing on Physiochemical Characteristics of Soybean Oil and Deodorizer Distillates

The present study aimed to evaluate the impact of industrial processing (neutralization/degumming, bleaching, and deodorization) on physicochemical characteristics of soybean oil and soybean oil deodorizer distillate (SBO-DD) collected from two different industries. The substantial impact of processing was observed on all physicochemical parameters except the iodine value (IV) and saponification value (SV). Gas chromatography-flame ionization detector (GC-FID) and Gas chromatography-mass spectrometry (GC-MS) analytical techniques were used for the quantification of individual fatty acids, sterols, and 3-monochloropropane diol (3-MCPD) ester. Among the fatty acids, palmitic and linoleic acids were present at higher concentrations in all processing stages. Among sterols, β-sitosterol was found to be higher (25.65 and#181;g/g) in crude soybean oil and reduced to 16.44 and#181;g/g after processing till the final deodorization stage. 3-MCPD ester was developed during the neutralization/degumming process and further increased during bleaching and deodorization up to 315 and#181;g/kg, respectively. SBO-DD was found to be a rich source of total and individual sterols as compared to crude or processed soybean oil. High free fatty acid (FFA) level in deodorizer distillate indicated that SBO-DD is a potential source of biodiesel production.

Immobilization of Lipozyme TL 100L for methyl esterification of soybean oil deodorizer distillate.

An immobilization method for binding cross-linked enzyme aggregates of Lipozyme TL 100L on macroporous resin NKA (CLEA-TLL@NKA) was developed in this study. The esterification activity of CLEA-TLL@NKA reached 6.4 U/mg. The surface structure of immobilized lipase was characterized by scanning electron microscopy. Methyl esterification reaction of soybean oil deodorizer distillate (SODD) was catalyzed by CLEA-TLL@NKA, which the conversion rate reached 98% and its activity retained over 90% after 20 batches of reaction. Compared with the commercial enzyme Lipozyme TLIM, half-life (t 1/2) of CLEA-TLL@NKA increased by 25 times and the catalytic activity increased by approximate 10 times. Thus, CLEA-TLL@NKA had high catalytic activity, good operational stability, and potential industrial application in the field of oil processing.

Preparation of high purity squalene from soybean oil deodorizer distillate with the combination of macroporous resin and thin-film evaporation coupling distillation

ABSTRACTIn this study, the combination of macroporous adsorbent resins (MARs) and thin-film evaporation coupling distillation (TFECD) was studied systematically, with aim to obtain high value-added squalene from soybean oil deodorizer distillate (SODD). Five types of resins (X-5, D-101, D4020, DM301, and AB-8) were first used to evaluate the adsorption/desorption properties of squalene. D101 resin exhibited higher adsorption/desorption capacities and desorption ratios for squalene based on static adsorption results among the tested resins. We further investigated the adsorption kinetics, isotherms, and thermodynamics with D101 resin as adsorbent. The adsorption of squalene on D101 was best fitted to pseudo-second-order kinetic model and the Langmuir equation. The dynamic adsorption and desorption indicated that similar results were observed in the static adsorption test. The purity of squalene was increased from 7.5 to 82.5% with the recovery up to 88.5% after separation on D101 column. The resin-refined sample was directly subjected to TFECD purification. Under optimized process parameters, the final product with purity of 98.5% and recovery yield of 76.5% was confirmed by high-performance liquid chromatography (HPLC) analysis. The present study provided an effective method for large-scale production of high purity squalene.

Functional Foods from Soybean Oil Deodorizer Distillate using Candida Rugosa and Candida Antarctica lipases

Functional Foods from Soybean Oil Deodorizer Distillate using Candida Rugosa and Candida Antarctica lipases

Extraction of Tocopherol from Soybean Oil Deodorizer Distillate by Deep Eutectic Solvents

Natural tocopherols have strong antioxidant and physiological functions, which are mainly produced from vegetable oil deodorized distillates. In this work, a simple and green solvent extraction method based on deep eutectic solvent has been developed to simultaneously extract three isomers of tocopherols (α, γ and δ-tocopherols) from soybean oil deodorizer distillate (SODD). The key factor to affect the solvent extraction efficiency was proposed that phenolic deep eutectic solvents interacted with targeted tocopherols mainly through π-π bonds interaction. This sustainable extraction process included two steps. Firstly, total tocopherols were extracted from SODD at room temperature by phenolic deep eutectic solvent composed of ChCl and p-cresol. Subsequently, tocopherols were successfully separated from deep eutectic solvent phase by re-extraction with n-hexane, and tocopherols products could be simply recovered. Under the optimum extraction conditions, the extraction efficiency of total tocopherols (α, γ and δ-tocopherols) from SODD was 77.6% after extraction with phenolic deep eutectic solvent.

Optimization of the recycle structure of multiple stages molecular distillation

In cases when the separation achieved by one molecular distillation stage is not sharp enough, it is resorted to multiple stage schemes. This brings the issue of how to recycle the intermediate streams to optimize the process. The present paper proposes to use the source-sink assignment methodology to decide the recycle structure. The counter current scheme is also taken into account because it is usually regarded as the design of choice to recycle streams. The approach was applied to optimize the recycle structure of a two stages process for the separation of free fatty acids from soybean oil deodorizer distillate, to get a concentrate of tocopherols in the residual stream, within specification of acidity. The counter current scheme was also implemented. For this case study the optimal recycle structure gets 10% more product with a profit 0.6% larger than the counter current scheme, even if it has larger operative and investment costs. So, in this particular case, the reward for using a rigorous methodology was not that significant. However, the approach proposed here is systematic and necessarily leads to a structure with a performance greater than or equal to any other, because the superstructure explored includes all of them.

Intensification of biodiesel production using dual-frequency counter-current pulsed ultrasound

Biodiesel production from soybean oil deodorizer distillate intensified by dual-frequency counter-current pulsed ultrasound and the kinetics were studied. Results indicated that the biodiesel conversions enhanced by single-frequency were lower than those enhanced by dual-frequency. For dual-frequency, the biodiesel conversion of SMM was higher than those of SQM. The biodiesel conversion of the combination of 20/28kHz is the highest. The effects of 20/28kHz SMM on biodiesel production were studied and optimal conditions were: methanol to triglyceride molar ratio 8:1, catalyst content 1.8%, the water content in feedstock should be less than 0.4%, the acid value of feedstock should be less than 2mgKOH·g−1, the biodiesel conversion could reach 96.3%.The kinetics of SMM and SSPU were studied and results showed that the transesterification reaction was pseudo-second order and the energy activation obtained by SMM and SSPU were 18.122kJ·mol−1 and 26.034kJ·mol−1, respectively. These results showed that transesterification reaction intensified by SMM is easier to take place than SSPU.

Production of esters from soybean oil deodorizer distillate in pressurized ethanol

The aim of this study was to obtain esters from soybean oil deodorizer distillate (SODD) in pressurized ethanol without the use of a catalyst. Experiments were carried out to evaluate the effects of the operating variables (pressure, temperature, residence time and ethanol to free fatty acids molar ratio) using a minimum factorial experimental design. The results indicate that increasing the temperature, pressure and residence time in the reactor enhanced the conversion of free fatty acids (FFA) while increasing the ethanol to FFA molar ratio decreased the conversion. The experiment carried out under optimum conditions (20MPa, 275°C, 20min and ethanol to FFA molar ratio of 7:1) reached ~87% of FFA conversion. The reaction kinetics was investigated at different temperatures and the results obtained reveal that a high rate of FFA consumption and conversions close to the thermodynamic equilibrium were quickly reached. At high temperatures (325 and 350°C) the conversion decreased with increasing residence time, indicating that the reverse reaction occurred. The reaction in two steps increased the FFA conversion, indicating that the conversions obtained were close to the thermodynamic equilibrium and the removal of water between the steps shifted the equilibrium, making it possible to achieve higher FFA conversion and ester yields.

Biodiesel production from soybean oil deodorizer distillate usingcalcined duck eggshell as catalyst

Biodiesel production from soybean oil deodorizer distillate (SODD) using calcined duck eggshell (DES) as catalyst was studied. An inexpensive and environment-friendly catalyst was prepared from waste DES which is a source of calcium carbonate. The calcium carbonate could be changed to calcium oxide (CaO) under high temperatures. The obtained CaO was characterized by X-ray diffraction (XRD), Fourier Transmission Infrared Spectra (FT-IR), Scanning Electron Microscopy (SEM). XRF was used to determine the elemental composition of the catalyst. BET analysis was performed to determine specific surface area, pore volume and particle size of the catalysts. Results showed that at 800°C and 900°C the calcium carbonate in DES was changed to CaO. The pre-esterification of SODD was conducted under the following conditions: H2SO4 concentration (v/w, based on oil weight) 1.5%, methanol to oil molar ratio 12:1, reaction time 120min and reaction temperature 60°C. Thephytosterols were removed by cooling down step by stepand temperature steps were 15°C, 5°C, −5°C. The process of biodiesel production from pre-esterified SODD using the obtained CaO as catalyst was studied and the optimal conditions were: calcination temperature of 900°C, catalyst amount of 10wt.%, methanol to oil ratio of 10:1, reaction temperature of 60°C and reaction time of 80min and the biodiesel yield was 94.6% at these conditions. The reusability of the DES-derived catalyst was tested and the results showed that the biodiesel yield was above 80% after five times usage and was lower than 60% after 8 times usage.

Factores que influyen en el contenido de escualeno, fitoesteroles totales y esterificados en el subproducto ácidos grasos destilados de soya para su potencial aprovechamiento

Una necesidad actual de la industria de extracción y refinación de aceite vegetal es la reducción y/o explotación de sus subproductos. Uno de estos, conocido como Ácidos Grasos Destilados de Aceite de Soya (AGDAS), resulta potencialmente valioso para la industrias alimentaria, farmacéutica y cosmética por la presencia de compuestos con actividad biológica favorable como fitoesteroles y escualeno, los primeros como agentes hipocolesterolemiantes y el escualeno como emoliente y humectante. En este trabajo, mediante Cromatografía de Gases se determinó el contenido de escualeno y fitoesteroles libres y esterificados para evaluar la viabilidad de aprovechamiento de AGDAS como fuente de dichos compuestos y establecer la influencia de algunos factores en la composición del mismo. AGDAS representa una fuente viable de fitoesteroles totales con 14.92% p/p, no así de escualeno con 1.75% p/p. La concentración de escualeno está influenciada por la procedencia del grano y la condición de cultivo, mientras que la de fitoesteroles esterificados por el grado de calidad y condición de cultivo. Ninguno de los factores influyó en el contenido de fitoesteroles totales. Esto permite establecer que la composición del subproducto AGDAS no es constante y se justifican protocolos como el de este estudio para su caracterización con fines de aprovechamiento.