Oil Deodorizer Distillate Research Articles

Plasticization of Polylactide Using Biobased Epoxidized Isobutyl Esters Derived from Waste Soybean Oil Deodorizer Distillate

Plasticization of Polylactide Using Biobased Epoxidized Isobutyl Esters Derived from Waste Soybean Oil Deodorizer Distillate

Effects of Palm Oil Deodorizer Distillate on the Ruminal Environment of Sheep.

This study aimed to assess the impact of palm oil deodorizer distillate (POD) on the ruminal environment, including (i) microbial community, (ii) ruminal degradability, and (iii) apparent digestibility in sheep. The data used were derived from twenty rumen-cannulated sheep fed five isoproteic and isofiber diets based on elephant grass (Pennisetum purpureum Schum. cv. Roxo) silage supplemented with 0, 25, 50, 75, or 100 g kg-1 POD on a dry matter (DM) basis. Rumen fluid samples were collected three hours after feeding directly from the ventral sac of the rumen via a cannula and then subjected to DNA extraction, which was subsequently used for 16S rDNA amplification, followed by sequencing and diversity analysis. In this study, the microbial diversity was dominated by Bacteroidetes and Firmicutes, followed by Euryarchaetoa, Actinobacteria, and Tenericutes, in the ruminal environment, and was slightly modified when supplemented with the POD up to 100 g/kg (10%), leading to only a slight decrease in the diversity index. The ruminal degradability, ruminal fermentation parameters, and apparent digestibility were slightly compromised by the inclusion of up to 25 g of POD per kg of DM, and larger inclusions interfered with the ruminal degradability of fibrous fractions and the apparent digestibility of dry matter. This lipid supplement showed good results for feeding sheep and is an inexpensive and abundant alternative in the regional market.

Degradation of polycyclic aromatic hydrocarbons in oil deodorizer distillates: Kinetics, degradation product identification and toxicity

Polycyclic aromatic hydrocarbons (PAHs) with strong carcinogenicity can cause great threat to human health. However, limited research has focused on the degradation of PAHs in oil deodorizer distillates (ODDs). In this study, E. coli expressing plasmid PodAB were applied in ODD samples to degrade PAHs and compared with white rot fungi (WRF). Prediction model for reactive sites of PAHs and the toxicity of degradation products were developed using density functional theory (DFT) calculations and quantitative structure–activity relationship (QSAR), respectively. The results indicated that the degradation rate of PAHs in ODD reached up to 59.28% using E. coli with the co-expression of pBRCD, which provided the electron carrier. The prediction results using nucleophilic index was consistent with the identification results of GC-MS, which may be more suitable for predicting the PAH oxidation products. Moreover, the R2 of developed QSAR reached 0.8976 for the correlation coefficient between predicted and observed toxicity value, which can be applied to predict the toxicity of degradation products. This work proposes a potential tool for PAH removal in ODD as well as a simple method for predicting PAH oxidation products as well as their toxicity.

Lowering polycyclic aromatic hydrocarbon concentrations in vegetable oil deodorizer distillates and enhancing its utilization by graphene composites

Vegetable oil deodorizer distillates (VODDs), which are the main source of natural tocopherol, are easily contaminated by polycyclic aromatic hydrocarbons (PAHs), and pose health threats to human beings. To remove 16 priority-control PAHs in VODD, three graphene (GR) composites, including TiO2-GR, sepiolite-GR and Fe3O4-GR, were prepared. PAH concentrations and removal rates were determined using gas chromatography-mass spectrum (GC-MS). Additionally, density functional theory (DFT) calculation was conducted to simulate and illustrate PAH adsorption on GR composites. The results indicated that the highest BaP removal rate was given to TiO2-GR with 90.37 ± 3.23 % after 2 h in standard solution. The adsorption followed the pseudo-first order kinetic, with the constant of −0.0141. In contrast, 61.62 ± 7.88 % total PAHs were removed in VODD using TiO2-GR. Moreover, DFT calculation verified that the strongest adsorption effect occurred between TiO2-GR and PAHs, with the adsorption energy of −2.69 eV. Additionally, GR composite morphology would be changed when LPAH concentrations are higher than 30 μg kg-1. The results also indicated the retention rates tocopherol ranged from 91.91 ± 1.92 % to 99.22 ± 0.88 %. This study firstly provides a useful tool for PAH removal in VODDs while retaining tocopherol. Moreover, it will increase the understanding of adsorption process between PAHs and GR composites.

Application of pilot‐scale molecular distillation for enrichment of phytonutrients from a novel deodorizer distillate of the margarine and shortenings industry

AbstractBackgroundA wiped‐film molecular distillation (WFMD) pilot plant was used to evaluate process conditions for enriching phytonutrients (PN) from a novel vegetable oil deodorizer distillate (VODD) of the margarine and shortenings industry. This byproduct results from the incorporation of new blends of vegetable oils, such as soybean and palm oil, making it of interest due to its distinct chemical composition and matrix, which differ from those of deodorizer distillates studied previously. The significance of the present investigation is related to the properties of the oil blend, requiring the establishment of new process conditions for this specific VODD. Experimental design was used to evaluate the WFMD process variables, with the aim of removing free fatty acids and enabling eight PN to be concentrated in the reprocessing stages.ResultsThe product obtained after three WFMD stages presented a fivefold increase in the total PN concentration, compared to the raw material. Notably, the procedure provided enrichment ratios of 7.2‐fold for total tocopherols (including α‐, β‐, λ‐ and δ‐tocopherols), 4.5‐fold for total phytosterols (including campesterol, stigmasterol and β‐sitosterol) and 1.2‐fold for squalene, together with a deacidification efficiency of 78.93%.ConclusionThe proposed process provided significant concentration gains for all eight PN evaluated, resulting in a value‐added product. These excellent results were achieved using only three WFMD stages, without any need for additional processing steps. The data obtained at the pilot scale provide valuable insights for predicting the scalability of the process and facilitating potential industrial implementation. © 2023 Society of Chemical Industry.

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.

Determination, exposure and risk assessment of PAHs in natural vitamin E isolated from vegetable oil industry

ABSTRACT Natural vitamin E, which is mainly extracted from vegetable oil deodoriser distillate (VODD), is likely contaminated by carcinogenic polycyclic aromatic hydrocarbons (PAHs). A total of 26 commercial vitamin E products from six countries were investigated for 16 EPA PAHs using QuEChERS combined with gas chromatography triple quadrupole mass spectrometry (GC-QQQ-MS). The concentrations of total PAHs in the samples ranged from 46.5 μg kg−1 to 215 μg kg−1, while the concentrations of PAH4 (BaA, Chr, BbF and BaP) ranged from 4.43 μg kg−1 to 20.1 μg kg−1. Risk assessment indicates that maximum intake of PAHs is 0.2 mg day−1, which is less than the LD50 and no observed adverse effect levels (NOAEL) of PAHs. However, chronic carcinogenicity of PAHs needs to be considered. The results suggested that PAH concentrations as well as toxicity equivalent should be considered as important indicator of risk of vitamin E products.

Optimization of Vitamin E Extraction from Rice Bran Oil Deodorizer Distillate using Response Surface Methodology

Rice bran oil deodorizer distillate (RBODD) is the low valuable secondary product of refinery rice bran oil. However, RBODD contains bioactive compounds such as vitamin E, gamma-oryzanols, and phytosterols. To increase value of vitamin E obtained from underutilized product, tocopherols and tocotrienols were extracted from RBODD using ethanol followed by a freezing step. The response surface method (RSM) is known as a potential tool for optimizing processing parameters in order to save time, energy, and chemical material. In current study, vitamin E extract (VEE) was extracted using ethanol and response surface method (RSM) was employed to investigate the optimum condition. The ratio of RBODD: ethanol (1:5, 1:10, and 1:15) and the incubation temperature (0, -20, and -40℃) of vitamin E extraction were used to design the experiment using a central composite design (CCD). Once the optimization process was completed, the RSM was executed using the following 5 responses simultaneously: VEET3, VEEToc, VEETot, RecoveryVEE, and YieldVEE. Results showed that values of each parameter were VEET3 (10.69-89.60 mg/g), VEEToc (2.85-23.37 mg/g), VEETot (13.53-112.97mg/g), RecoveryVEE (16.15-134.76%), and YieldVEE (12.64-44.48%). All model predictions were significant (p-value < 0.05), with non-significant lack of fit (> 0.05). In addition, the values of R2 and R2(Adj) of model were in the range of 0.922-0.988 and 0.893-0.982, respectively. According to these findings, response values were associated with RBODD:ethanol ratio and the incubation temperature. The ratio 1:9.5 (RBODD: Ethanol) and incubation temperature at -26.5 ℃ provided the optimal condition for vitamin E extraction from RBODD. At this optimum condition, it was determined that the predicted responses for VEET3, VEEToc, VEETot, RecoveryVEE, and YieldVEE were 81.87 mg/g, 23.70 mg/g, 103.64 mg/g, 123.63 %, and 20.05%, respectively. The obtained product with high content of tocopherol and tocotrienol can be used as ingredient in food as well as pharmaceutical applications.

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

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.

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.