Deodorizer Distillate Research Articles

New Strategies for the Valorisation of Deodorizer Distillates of Vegetable Oils Refining in a Sustainable Circular Economy Development

New Strategies for the Valorisation of Deodorizer Distillates of Vegetable Oils Refining in a Sustainable Circular Economy Development

Preparation and Utilization of Hydroxyapatite-Supported Na and CaO–CeO2 Catalysts for Biodiesel Production Using Vegetable Oil Deodorization Distillate as Raw Material

Preparation and Utilization of Hydroxyapatite-Supported Na and CaO–CeO2 Catalysts for Biodiesel Production Using Vegetable Oil Deodorization Distillate as Raw Material

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.

Chromatographic evaluation of tocols and sterols of processed canola oil and deodorizerdistillate

Tocopherols and tocotrienols in the combined form are known as tocols. Changes of total and individual tocols and sterols concentration of canola oil and deodorizer distillate (DD) during different processing stages were evaluated with the application of gas chromatography (GC) and high-performance liquid chromatography (HPLC). For sterols analysis, GC coupled with flame ionization detector (FID) was used while tocols in canola oil samples and DD, normal phase (NP) HPLC was applied. The results of the present study indicated that levels of total and individual tocols and sterols content were decreased during processing (neutralization to deodorization). Deodorization was found to be the most effective process for the reduction of total sterols and tocols as 55.9% and 34.2%, respectively. A high amount of tocols and sterols was observed in DD. Among tocols and sterols; beta tocopherol (β-T) and β-sitosterol were found to be in greater concentration 53.97% and 31.82%, respectively. Therefore, DD could be used as a valuable byproduct in the cosmetics and food industries.

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.

Immobilization of Amano AK Lipase from Pseudomonas fluorescens on Novel Silk Microfiber using Oxone®: Parameter Optimization for Enzymatic Assays and use in Esterification of Residual Palm Oil

Background: Biodiesel has been shown to be effectively produced by immobilized enzymatic catalysts. The selection of support material is a prominent factor for obtaining an efficient lipase. Silk fibroin (SF) is a natural polymer produced by glands of some arthropods, especially by the Bombyx mor, attracting attention for immobilization of lipase. Objective: This paper presents a novel method to obtain silk microfibers (SMF) from Oxone® salt in water, used as support for Amano AK lipase from Pseudomonas fluorescens in biodiesel production from deodorization distillate of palm oil (DDPO). Method: The oxone® salt in the presence of Ca2+ ions acts as a mineralizing agent in the peptide bonds present in silk fibroin, altering some of its physical and chemical properties, such as zeta potential, crystallinity, micro-morphology, infrared spectroscopic profile, and showing formation or absence of SF original connections. Results: The modified support was tested as a support alternative for the immobilization of Amano AK lipase from Pseudomonas fluorescens. Enzyme activity values indicated that lipase immobilization on SMF was efficient as a heterogeneous catalyst in the esterification of DDPO (deodorization distillate palm oil). Conclusion: The effect of some reaction parameters, such as catalyst concentration, molar ratio, temperature, and reaction time, was studied to optimize the conditions for maximum conversion of DDPO (40.5%).

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

Separation of squalene from olive oil deodorizer distillate using short‐path molecular distillation

AbstractSqualene was recovered from an olive oil deodorizer distillate (OODD) containing 40% of squalene by a two‐step process. The first step was to esterify the free fatty acids (FFAs) to make them less volatile. The second step was to separate the squalene by molecular distillation. The best esterification conditions were found to be 190°C and 360 min, where FFA content of the reaction mixture was reduced from 49.3% to 7.9%, however, an inevitable squalene loss (30%) was also observed due to a discontinuous operation. The remaining squalene (28%) in the esterified mixture was then distilled using a molecular distillation unit at elevated temperatures (190–230°C) and pressures (0.05–5 mmHg). When the temperature and vacuum during distillation increased, FFA content in the distillate reduced while distillate yield and squalene purity increased. The highest distillate yield (27.7%) and squalene purity (98.1%) were obtained at the highest applied temperature (230°C) under the lowest absolute pressure (0.05 mmHg), where FFA content of distillate was measured as 1.8%. High percentage of squalene (95%–98%) could be distilled at 230°C between 0.05 and 0.5 mmHg absolute pressures. The overall squalene recovery after all treatments was calculated as 68%.

Comparative screening of organic solvents, ionic liquids, and their binary mixtures for vitamin E extraction from deodorizer distillate

Although it is well known that solvent is one of the most important decision variables in liquid-liquid extraction processes, many previous studies focused on a specific class of solvents while neglecting alternatives. This work presents a comparative screening of two types of most extensively studied solvents, i.e., organic solvents (OS) and ionic liquids (ILs), as well as their binary systems for the extraction of vitamin E from methylated oil deodorizer distillates (modelled as a mixture of α-tocopherol and methyllinoleate). For this practically relevant task, the ternary liquid-liquid equilibria (LLE) of {OS or IL + α-tocopherol + methyllinoleate} are first calculated by use of the COnductor-like Screening Model for Real Solvents (COSMO-RS), after which the physical and environmental, health, and safety (EHS) properties of solvents are assessed to identify the top-ranked OS and ILs. To intensify the separation performance, binary solvent systems are also explored, where one of the pre-selected ILs is taken as the first solvent for α-tocopherol and an OS is screened as the second solvent for methyllinoleate. Then, the IL-OS combinations are investigated regarding their binary immiscibility and ranked with respect to the LLE performance in the quaternary system {IL + α-tocopherol + methyllinoleate + OS}. By comparing the extraction distribution coefficient and the selectivity of the top-ranked OS, ILs and IL-OS systems, the notable intensified performance of binary solvent system is proven.

Synthesis of Alpha Olefins: Catalytic Decarbonylation of Carboxylic Acids and Vegetable Oil Deodorizer Distillate (VODD)

Decarbonylation of carboxylic acids provides an effective protocol for producing alpha olefins; however, previous literature has focused on the palladium-bisphosphine catalysts and has only sporadically studied the palladium-monophosphine catalyst. To investigate the catalytic activity of the palladium-monophosphine catalyst on decarbonylation of carboxylic acids, new monophosphine ligands were synthesized (NP-1, NP-2, CP-1 and CP-2). By employing (1–3 mol%) palladium-naphthylphosphine catalysts, various carboxylic acids were converted into corresponding alpha alkenes with good yields and selectivity within a short period of time. Vegetable oil deodorizer distillate (VODD), which is a by-product from the vegetable oil refinery process, was found to be rich in free fatty acids and there is great interest in turning vegetable oil deodorizer distillate into value-added compounds. It is noteworthy that our catalytic system could be applied to convert vegetable oil deodorizer distillate (VODD) into diesel-like hydrocarbons in a good yield.

Process simulation of biodiesel production from vegetable oil deodorization distillate using hydrotalcite-hydroxyapatite as catalyst

In There are few simulation studies in the literature focusing on the production of biodiesel from vegetable oil deodorization distillate (VODD), a waste originating from the vegetable oil processing stage, using hydrotalcite-hydroxyapatite as a heterogeneous catalyst. In this study, the simulation process was performed using open interface software DWSIM® Version 6.3. The motivation relied on the positive performance of the catalyst during the experimental studies. So, in the simulator design, the lipid raw material, ethanol, and the catalyst were fed together in a CSTR-01 conversion reactor. The thermodynamic fluid package used for this process was the Non-Random Two-Liquid (NRTL) activity coefficient model. The process flowchart consisted of the reaction step (oil transesterification), and separation steps of the ethyl esters produced, excess ethanol and purification of biodiesel. As a result, different scenarios were simulated, using commercial soybean oil as a comparative form, different types of catalysts and different molar ratios of alcohol and VODD. Among the main differences between the simulated cases, it was demonstrated that the excess of alcohol (1:45) caused greater quantity of VODD consumption, and consequently the greater formation of ethyl esters (biodiesel), resulting higher conversions (> 95%). In addition, the results obtained confirmed the adequacy of VODD as a potential raw material to produce biodiesel, as it is relatively cheaper than edible oils and contributes to the use of waste. Thus, confirming that the chemical catalyst was able to form the main esters of fatty acids even using a residual raw material.

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.

Palm oil wastes as feedstock for lipase production by Yarrowia lipolytica and biocatalyst application/reuse.

Palm oil production chain generates a greasy residue in the refining stage, the Palm Oil Deodorizer Distillate (PODD), mainly composed of free fatty acids. Palm oil is also used industrially to fry foods, generating a residual frying oil (RFO). In this paper, we aimed to produce lipase from palm agro-industrial wastes using an unconventional yeast. RFO_palm, from a known source, consisted of 0.11% MAG + FFA, 1.5% DAG, and 97.5 TAG, while RFO_commercial, from a commercial restaurant, contained 6.7% of DAG and 93.3% of TAG. All palm oil wastes were useful for extracellular lipase production, especially RFO_commercial that provided the highest activity (4.9 U/mL) and productivity (465 U/L.h) in 75h of processing time. In 48h of process, PODD presented 2.3 U/mL of lipase activity and 48.5 U/L.h of productivity. RFO_commercial also showed the highest values for lipase associated to cell debris (843 U/g). This naturally immobilized biocatalyst was tested on hydrolysis reactions to produce Lipolyzed Milk Fat and was quite efficient, with a hydrolysis yield of 13.1% and 3-cycle reuse. Therefore, oily palm residues seem a promising alternative to produce lipases by the non-pathogenic yeastY. lipolytica and show great potential for industrial applications.

Novel Fast Chromatography-Tandem Mass Spectrometric Quantitative Approach for the Determination of Plant-Extracted Phytosterols and Tocopherols.

Phytosterols and tocopherols are commonly used in food and pharmaceutical industries for their health benefits. Current analysis methods rely on conventional liquid chromatography, using an analytical column, which can be tedious and time consuming. However, simple, and fast analytical methods can facilitate their qualitative and quantitative analysis. In this study, a fast chromatography-tandem mass spectrometric (FC-MS/MS) method was developed and validated for the quantitative analysis of phytosterols and tocopherols. Omitting chromatography by employing flow injection analysis—mass spectrometry (FIA-MS) failed in the quantification of target analytes due to analyte-to-analyte interferences from phytosterols. These interferences arise from their ambiguous MS fingerprints that would lead to false identification and inaccurate quantification. Therefore, a C18 guard column with a 1.9 µm particle size was employed for FC-MS/MS under isocratic elution using acetonitrile/methanol (99:1 v/v) at a flow rate of 600 µL/min. Analyte-to-analyte interferences were identified and eliminated. The false peaks could then be easily identified due to chromatographic separation. In addition, two internal standards were evaluated, namely cholestanol and deuterated cholesterol. Both internal standards contributed to the observed analyte-to-analyte interferences; however, adequate shift in the retention time for deuterated cholesterol eliminated its interferences and allowed for an accurate quantification. The method is fast (1.3 min) compared to published methods and can distinguish false peaks observed in FIA-MS. Seven analytes were quantified simultaneously, namely brassicasterol, campesterol, stigmasterol, β-sitosterol, α-tocopherol, δ-tocopherol, and γ-tocopherol. The method was successfully applied in the quantitative analysis of phytosterols and tocopherols present in the unsaponifiable matter of canola oil deodorizer distillate (CODD). β-sitosterol and γ-tocopherol were the most abundant phytosterols and tocopherols, respectively.

Chromatographic evaluation of tocols and sterols of processed canola oil and deodorizer distillate.

Tocopherols and tocotrienols in the combined form are known as tocols. Changes of total and individual tocols and sterols concentration of canola oil and deodorizer distillate (DD) during different processing stages were evaluated with the application of gas chromatography (GC) and high-performance liquid chromatography (HPLC). For sterols analysis, GC coupled with flame ionization detector (FID) was used while tocols in canola oil samples and DD, normal phase (NP) HPLC was applied. The results of the present study indicated that levels of total and individual tocols and sterols content were decreased during processing (neutralization to deodorization). Deodorization was found to be the most effective process for the reduction of total sterols and tocols as 55.9% and 34.2%, respectively. A high amount of tocols and sterols was observed in DD. Among tocols and sterols; beta tocopherol (β-T) and β-sitosterol were found to be in greater concentration 53.97% and 31.82%, respectively. Therefore, DD could be used as a valuable by-product in the cosmetics and food industries.

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.