Oil Deodorizer Distillate Research Articles

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.

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.

Solid phase extraction of β-sitosterol and α-tocopherol from sunflower oil deodorizer distillate using desilicated zeolite

In this study, the efficiency of using zeolite-based adsorbents in a solid phase extraction (SPE) procedure of α-tocopherol and β-sitosterol isolation from Sunflower Oil Deodorizer Distillate (SuDOD) with­out pre-treatment was investigated. The results showed that 99.2% α-tocopherol and 97.3% β-sitosterol were suc­cessfully isolated as pure fractions from SuDOD, when desilicated ZSM-5-type zeolite (DSiZSM-5) was used as adsorbent on a SPE. A simple and rapid HPLC method for simultaneous α-tocopherol and β-sitosterol analysis was developed and validated according to AOAC guidelines. It was found that the inclusion of a DSiZSM-5 SPE step increased the precision of the α-tocopherol and β-sitosterol analysis. In conclusion, DSiZSM-5 zeo­lite was proven to be an efficient adsorbent which can be used not only for the recovery of α-tocopherol and β-sitosterol from SuDOD in industrial scale, but also in a laboratory scale clean-up method prior to the analysis of α-tocopherol and β-sitosterol.

Glycerolysis of free fatty acid in vegetable oil deodorizer distillate catalyzed by phosphonium-based deep eutectic solvent

Abstract Esterification of free fatty acids in a low-grade oil with glycerol, the by-product of transesterification, has been proposed as one possible method to reduce the cost of raw materials for biodiesel production. The glycerolysis reaction recycles the byproduct glycerol to create a much more efficient and cost-effective process. However, the glycerolysis reaction involves challenges, including its requirement of high temperature. This study is the first to apply the deep eutectic solvent (DES) as a catalyst for glycerolysis reaction to convert free fatty acid (FFA) in vegetable oil deodorizer distillate (VODD) being a waste product from the oil refining process into glycerides. The effects of temperature, catalyst dosage, and time on the esterification efficiency of fatty acid conversion were explored. The reaction progress and product solubility were studied by FT-IR and GC. The results revealed that the reaction reached equilibrium at an approximate free fatty acid (FFA) conversion of 90%. The reaction was a second-order reversible reaction, using 8 wt% catalyst loading lowered activation energy to 58.80 J/mol. The optimum condition was determined as 160 °C, 5 wt% DES loading, and 10 min reaction time.

Modelling and simulation of supercritical CO2 extraction of bioactive compounds from vegetable oil waste

Deodorizer distillates are waste by-product from vegetable oil industries. It has excellent potential as a source of bioactive compounds. Therefore, the aim of this study was to model the thermodynamic phase equilibrium and optimize the supercritical CO2 extraction processes for concentrating valuable minor components from rapeseed oil deodorizer distillates (RODD). The extraction was done in a countercurrent extraction column at pressure (35−40 MPa), temperature (313 K) and solvent to feed mass ratio (S/F) of 5. The raw material employed was initially saponified. Investigating the extraction process, representing phase equilibria behavior of the multicomponent oil-type material/CO2 mixture and prediction the steady-state efficiency of the extractor was done by using the Stryjek–Vera Peng–Robinson equation of state as a thermodynamic model for the experimental bubble pressures and vapor compositions. The extraction of β-sitosterol and vitamin E in the saponified RODD at predicted conditions showed a recovery of 76 wt% with a purity of 60 wt% and a recovery of 85 wt% with a purity of 75 wt% respectively. Furthermore, the use of a modified sample increased the phytosterol and tocopherol efficiency and purity. The absolute average relative deviation between the theoretical and experimental was within the range of 1–12%, which is considered as a good agreement. The coupling of thermodynamic modeling with experimental work offered an efficient and rapid tool for analyzing the viability of the supercritical extraction.

Extraction of phytosterols and tocopherols from rapeseed oil waste by supercritical CO2 plus co-solvent: A comparison with conventional solvent extraction

In the present study, modified extraction methods using supercritical CO2 were investigated in order to obtain high-added value compounds from rapeseed oil deodorizer distillate and comparisons were done with modified Soxhlet extraction (solvent extraction + silica). For supercritical fluid extraction (SFE), the optimal extraction parameters were temperature of 40 °C, pressure of 350 bar (for phytosterols), 400 bar (for tocopherol), 5 wt% ethanol as co-solvent, and saponification pretreatment. The optimized SFE procedure led to the recovery of three main phytosterols (50 wt % β-sitosterol, 23.91 wt % Brassicasterol, and 36.25 wt % Campesterol) and only α-tocopherol. Moreover, there was no synergistic effect with saponification pretreatment + co-solvent and the efficiency and concentration of target compounds were less than supercritical CO2 + co-solvent. Also, comparative Data showed that the efficiency of phytosterols and tocopherols was approximately three times higher (p < 0.05) in SFE relative to modified Soxhlet extraction. Furthermore, the use of ethanol (5 wt %) as co-solvent, improved phytosterols and tocopherol efficiency and purity. The SFE technique offers various advantages over the modified Soxhlet extraction technique, including increasing the solubility of tocopherols and sterols by using CO2+ co-solvent, minimized usage of toxic organic solvents and increased purity of extracted products.

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.

Solid-phase extraction of phytosterols from rapeseed oil deodorizer distillates with magnetic graphene oxide nanocomposite

A fast and facile method was employed for the synthesis of magnetic graphene oxide (MGO). The synthesized MGO is characterized by different techniques and used as a solid-phase adsorbent for the extraction of β-sitosterol from rapeseed oil deodorizer distillates (RODD) followed by gas chromatography-mass spectrometry analysis. Several parameters affecting the extraction efficiency, including the amount of adsorbent, extraction time and temperature, desorption solvent and desorption time, were investigated. The procedure exhibited desirable extraction efficiency within 30 min at 35 °C. Recoveries higher than 80% were obtained with acetone as eluent and the method was successfully applied to concentrate the β-sitosterol in RODD CO2-supercritical extract. Compared to C18-silica and graphitic carbon, the composite showed satisfactory results for the extraction of β-sitosterol from oil samples.

Increased quality of in natura and cryopreserved semen of water buffaloes supplemented with saturated and unsaturated fatty acids from the palm oil industry.

Ruminant energy supplementation with vegetable oils or fats has been standing out worldwide and oil palm processing has been receiving growing interest. This study assessed the effect of supplementation with saturated and unsaturated fatty acids from the palm oil industry on the lipid profile of seminal plasma and of the sperm membrane, as well as on the morphological and functional characteristics of raw and cryopreserved buffalo semen. Twelve purebred Murrah bulls (Bubalus bubalis) were assigned to the experimental groups and fed diets for 120 days with no added lipids (CONT, four bulls), or with an extra amount of 3% lipids from crude palm oil (PALM, four bulls), or from palm oil deodorizer distillate (PODD, four bulls). Semen was collected and cryopreserved every 15 days. The lipid composition of membranes and semen quality were determined after collections. Lipid supplementation did not impact feed intake (P>0.05). Diet enrichment with PALM increased the linoleic acid (C18:2,ω6) in seminal plasma. Lipid supplementation did not increase the polyunsaturated fatty acids in the sperm membrane composition, but significantly increased the lignoceric acid (C24:0). Cryopreserved semen of the supplemented bulls presented higher progressive motility (60.2 vs. 67.9 vs. 65.2%; P<0.05) and sperm viability detected by eosin-nigrosin staining (61.1 vs. 69.4 vs. 67.8%; P<0.05). Palm oil reduced major sperm defects in both raw (12.2 vs. 9.3 vs. 13.2%; P<0.0001) and cryopreserved semen (12.4 vs. 9.4 vs. 11.2%; P<0.0001). The lipids added to the diet did not impact the population of spermatozoa with intact plasma and acrosomal membranes (PI-/PSA-), but significantly increased the percentage of spermatozoa with high mitochondrial potential (25.6 vs. 31.5 vs. 32.0%; P=0.008). The results suggest that lipid supplementation based on crude palm oil or palm oil deodorizer distillate can be safely used to feed buffalo bulls and may increase sperm attributes related to male fertility.

Investigation of biodiesel from Canola oil deodorizer distillate using dual biocatalyst

Depleting nature of nonrenewable energy sources and continuous environmental tribulations make the mankind to think differently regarding alternative renewable energy sources. In this regard, present research investigation contributes biodiesel from canola oil deodorizer distillate (CODD) using Lipase AY Amano 30 (Candida rugosa) and Novozyme 40013 (Candida antarctica) in the presence of methanol. Initially the neutral glycerides present in CODD were hydrolysed using lipase Amano AY 30 in the presence of water. The hydrolysed CODD was then esterified with methanol using non-specific immobilized enzyme NS 40013 for the production of biodiesel. The characteristics of final product were compared with diesel fuel and it showed good results. This bioprocess technology using biohydrolysis and bioesterification is a novel technology for biodiesel production from cheap raw materials like CODD.

Techno-economic evaluation of squalene recovery from oil deodorizer distillates

The potential of squalene recovery from oil deodorizer distillates (ODD) via a combination of supercritical ethanol esterification, supercritical CO2-extraction and additional purification was assessed via detailed process simulations. The squalene yields and purity from olive, sunflower and soybean ODD were determined. The highest squalene yield and purity could be achieved starting from olive ODD (95gsqualenekg−1ODD, 99wt% pure), followed by soybean ODD (31gsqualenekg−1ODD, 98wt% pure) and sunflower ODD (24 gsqualenekg−1ODD, 98wt% pure). Apart from squalene, two more value-added products can be produced, i.e., high purity ethyl esters (>88wt%) and a mixture of tocopherols and sterols. On a scale of 1kTonneODD per year, all feedstocks demonstrate economical potential in Europe. Even more, a flexible process configuration could be designed which is suitable for the treatment of the different feedstocks.

Determination of Parent and Oxygenated Polycyclic Aromatic Hydrocarbons (PAHs) in Waste Cooking Oil and Oil Deodorizer Distillate by GC–QQQ–MS

Abstract Background: Polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) are classes of contaminants that are present in the environment and food. They pose a great threat to human health because of their carcinogenicity and mutagenicity. Very few studies have focused on their concentration in waste cooking oil (WCO) and oil deodorizer distillate (ODD). Objective: This study aimed (1) to design a reliable method to determine 16 PAHs and 4 OPAHs in both WCO and ODD and (2) to determine and analyze PAH and OPAH concentrations in actual samples to provide references for further research. Method: The PAH determination approach included double liquid–liquid extraction, double solid-phase extraction, and GC–triple quadrupole tandem MS determination. Oxidation indices were determined by titrimetry. Results: The method reached good linearity (R2 &amp;gt; 0.99) and an acceptable recovery rate (55.01–126.16% for WCO and 57.48–128.97% for ODD). Ten WCO and five ODD samples were determined, and the total concentration of 16 PAHs varied from 16.34 to 239.01 and 101.08 to 198.04 μg/kg in WCO and ODD, respectively. Among the 16 PAHs, three-ring PAHs typically contributed the most. It was also found that the acid value has a strong correlation with the concentration of OPAHs, probably because of the contribution of free fatty acids to OPAH formation. Conclusions: The proposed method was effective in the analysis of PAHs and OPAHs in WCO and ODD.

Analysis of PAHs in oily systems using modified QuEChERS with EMR-Lipid clean-up followed by GC-QqQ-MS

Polycyclic aromatic hydrocarbon (PAH) analysis in oily matrices is a great challenge that needs improvements both in efficiency and environmental sustainability. In this study, a method based on QuEChERS and gas chromatography-quadrupole tandem mass spectrometry (GC-QqQ-MS) was established. The method was based on EMR-Lipid as the dispersed solid phase adsorbent and acetonitrile: acetone (3:2, v/v) as the extraction solvent. The recovery of 16 PAHs reached 66.72–112.87%; the RSD was less than 8%, and the LOD and LOQ were lower than 0.13 μg/kg and 0.43 μg/kg, respectively. Compared to the ISO 15753 method, our method reduced the pretreatment time by 2/3 and improved the recovery of heavy PAHs, such as fluoranthene, benzo[a]anthracene and benzo[b]fluoranthene. The low solvent usage of 10 mL was also environmentally friendly for a high throughput basis. After verification, the method was successfully applied to determine the PAHs in 12 real oily samples, including waste frying oils (WFOs) and vegetable oil deodorizer distillates (VODDs). The PAH concentrations determined in the WFOs and VODDs ranged from 39.21 to 197.44 μg/kg and 1219.34–1482.25 μg/kg, respectively. Our work suggests that the proposed method can serve as an alternative approach for the efficient and precise determination of PAHs in edible oils and other oily systems as well as a potential analytical approach to evaluate PAHs in foods and drinks. Furthermore, the PAH data for the WFOs indicate that the PAH level should be introduced as a safety index for the obsoleting of frying oil.

Theoretical and experimental assessment of supercritical CO2 in the extraction of phytosterols from rapeseed oil deodorizer distillates

Phytosterols, a group of naturally occurring compounds found in plant cell membranes, are structurally similar to the body's cholesterol and compete with that for absorption in the digestive system leads to the reduction of its blood level. This work is focused on the applying supercritical fluid extraction to isolate phytosterols from rapeseed oil deodorizer distillate (RODD). A thermodynamic model, the Peng Robinson equation of state model, was applied to show phase equilibrium behavior of the multicomponent oil-type material CO2 mixture and optimize the supercritical extraction process parameters. The extraction of sterols in the saponified RODD sample at 35 MPa, 313 K, and solvent to feed mass ratio (S/F) of 5, showed a recovery of 76 wt% with a purity of 60 wt%. Furthermore, the use of ethanol (5 wt%) as co-solvent, increased the phytosterol efficiency and purity. By coupling experimental studies with thermodynamic modeling, supercritical extraction processes could be analyzed more efficiently and rapidly.

Determination of Parent and Oxygenated Polycyclic Aromatic Hydrocarbons (PAHs) in Waste Cooking Oil and Oil Deodorizer Distillate by GC-QQQ-MS.

Background: Polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) are classes of contaminants that are present in the environment and food. They pose a great threat to human health because of their carcinogenicity and mutagenicity. Very few studies have focused on their concentration in waste cooking oil (WCO) and oil deodorizer distillate (ODD). Objective: This study aimed (1) to design a reliable method to determine 16 PAHs and 4 OPAHs in both WCO and ODD and (2) to determine and analyze PAH and OPAH concentrations in actual samples to provide references for further research. Method: The PAH determination approach included double liquid-liquid extraction, double solid-phase extraction, and GC-triple quadrupole tandem MS determination. Oxidation indices were determined by titrimetry. Results: The method reached good linearity (R² > 0.99) and an acceptable recovery rate (55.01-126.16% for WCO and 57.48-128.97% for ODD). Ten WCO and five ODD samples were determined, and the total concentration of 16 PAHs varied from 16.34 to 239.01 and 101.08 to 198.04 μg/kg in WCO and ODD, respectively. Among the 16 PAHs, three-ring PAHs typically contributed the most. It was also found that the acid value has a strong correlation with the concentration of OPAHs, probably because of the contribution of free fatty acids to OPAH formation. Conclusions: The proposed method was effective in the analysis of PAHs and OPAHs in WCO and ODD.

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.

Development and Characterization of Liposomal Formulations Containing Phytosterols Extracted from Canola Oil Deodorizer Distillate along with Tocopherols as Food Additives.

Phytosterols are plant sterols recommended as adjuvant therapy for hypercholesterolemia and tocopherols are well-established anti-oxidants. However, thermo-sensitivity, lipophilicity and formulation-dependent efficacy bring challenges in the development of functional foods, enriched with phytosterols and tocopherols. To address this, we developed liposomes containing brassicasterol, campesterol and β-sitosterol obtained from canola oil deodorizer distillate, along with alpha, gamma and delta tocopherol. Three approaches; thin film hydration-homogenization, thin film hydration-ultrasonication and Mozafari method were used for formulation. Validated liquid chromatographic tandem mass spectrometry (LC-MS/MS) was utilized to determine the entrapment efficiency of bioactives. Stability studies of liposomal formulations were conducted before and after pasteurization using high temperature short time (HTST) technique for a month. Vesicle size after homogenization and ultrasonication (<200 nm) was significantly lower than by Mozafari method (>200 nm). However, zeta potential (−9 to −14 mV) was comparable which was adequate for colloidal stability. Entrapment efficiencies were greater than 89% for all the phytosterols and tocopherols formulated by all three methods. Liposomes with optimum particle size and zeta potential were incorporated in model orange juice, showing adequate stability after pasteurization (72 °C for 15 s) for a month. Liposomes containing phytosterols obtained from canola waste along with tocopherols were developed and successfully applied as a food additive using model orange juice.

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.