Low-cost Oils Research Articles

Validation of the Methods for the Non-Milk Fat Detection in Artificially Adulterated Milk with Palm Oil

Dairy products are among the most adulterated food products. Due to the current high price of milk fat, it has been replaced by low-cost oils, especially those oils that have the same fatty acid profile as milk fat. This study intends to confirm the lowest level of palm oil added to milk and validate various methods for detecting palm oil in milk, including gas chromatography, reverse-phase high performance liquid chromatography, and Fourier transform infrared. Different amounts of palm oil were prepared in the final liquid milk using five treatments of fresh milk cream and an emulsion of palm oil. The results of this study showed that the values of the saponification number decreased with the increase in the percentages of added palm oil. There was no decrease under the limits of the Egyptian standards until the addition of 50% palm oil. The iodine number is less sensitive than the saponification number in the detection of palm oil. Butyro refractometer reading is unable to detect the palm oil in milk. The fatty acid profile in milk determined by gas chromatography correlated well with the addition of palm oil. Furthermore, there is a positive relationship between the level of added palm oil and the β-sitosterol content as measured by reverse-phase high-performance liquid chromatography. There was no relationship between the behavior of the spectra resulting from Fourier transform infrared spectroscopy and the presence of palm oil.

Engineering caveolin-mediated endocytosis in Saccharomyces cerevisiae

As a potential substitute for fatty acids, common low-cost oils could be used to produce acetyl-CoA derivatives, which meet the needs of low-cost industrial production. However, oils are hydrophobic macromolecules and cannot be directly transported into cells. In this study, caveolin was expressed in Saccharomyces cerevisiae to absorb exogenous oils. The expression of caveolin fused with green fluorescent protein showed that caveolin mediated the formation of microvesicles in S. cerevisiae and the addition of 5,6-carboxyfluorescein showed that caveolae had the ability to transport exogenous substances into cells. The intracellular and extracellular triacylglycerol levels were then detected after the addition of soybean oil pre-stained with Nile Red, which proved that caveolae had the ability to absorb the exogenous oils. Lastly, caveolin for oils absorption and lipase from Bacillus pumilus for oil hydrolysis were co-expressed in the naringenin-producing Saccharomyces cerevisiae strain, resulting in naringenin production increasing from 222 mg/g DCW (dry cell weight) (231 mg/L) to 269 mg/g DCW (241 mg/L). These results suggested that the caveolin-mediated transporter independent oil transport system would provide a promising strategy for the transport of hydrophobic substrates.

Facile Synthesis of Catalyst Free Carbon Nanoparticles From the Soot of Natural Oils

The growth of carbon nanostructures from vegetable oils using a modified conventional approach is a simple and environmentally friendly technology with controllable features. The goal of this study is to develop a simple and environmentally friendly process for making carbon nanoparticles using commercially available, low-cost vegetable oils. The technique involves the controlled burning of “Mustard”, “Olive”, and “Linseed” oils using the traditional clay lamps and collecting the carbon soot on a ceramic plate. The prepared carbon nanoparticles were purified through sonication and subjected to characterization using powder X-ray diffraction, SEM, Fourier transformed infrared, Thermogravimetric and differential scanning calorimetric analyses. The average particle size of carbon nanoparticles as investigated by powder X-Ray Diffraction analyses was found to be 18, 24, and 57 nm for mustard, olive and linseed oils respectively. SEM analyses revealed the surface morphology of these carbon nanostructures as spherical particles. Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC) providing knowledge about the thermal stability of these carbon nanoparticles. The synthesized carbon nanoparticles were screened for antibacterial activities against different species (e.g., Pseudomonas aeruginosa, Streptococcus haemolyticus, Proteus refrigere and Staphylococcus aureus) and fruitful results have been obtained.

Sulfonated and cross‐linked polystyrene ultrafine fibers for the esterification of palmitic acid for biodiesel production

AbstractFor the need of green and sustainable development, a fibrous solid acid catalyst was developed for the transformation of low cost oils to biodiesel in an efficient and green manner. Polystyrene was electrospun into ultrafine fibers with mean diameter of ~1.34 μm, and then simultaneously cross‐linked and sulfonated in sulfuric acid/acetic acid mixed solvent with paraformaldehyde as the external cross‐linker. The cross‐linking and sulfonation degrees were controllable by changing the ratio of sulfuric acid/acetic acid. After sulfonation and cross‐linking, the solvent resistance, chemical structure, and composition of these fibers were separately characterized by scanning electron microscopy, infrared spectroscopy, and elemental analysis. At last, this novel fibrous solid acid catalyst was used to catalyze the esterification reaction of palmitic acid and methanol for biodiesel production. After optimizing the reaction conditions, this fibrous solid acid catalyst can catalyze the esterification of palmitic acid and methanol with the conversion up to 92% under mild reaction conditions. Moreover, due to the fibrous structure, this fibrous solid acid catalyst could be readily separated and reused.

Novel multi–SO3H functionalized ionic liquids as highly efficient catalyst for synthesis of biodiesel

Biodiesel is an attractive alternative to fossil fuels due to the energy and environmental concerns. In this paper, seven different multi –SO3H functionalized ILs based on the low-cost less-substituted amines, which contained massive sites for functionalization of sulfonic acid groups and further treatment of sulfonate-based anions, were prepared as catalysts with high acidity and desirable catalytic activity for the synthesis of biodiesel from the esterification of oleic acid with methanol. The physicochemical properties of these acidic ILs were characterized by a variety of analytical techniques such as FT-IR, EA, TGA, and the Brønsted acidity was well determined by UV–vis. Among the ILs prepared, [EDA-PS][P-TSA] showed the highest catalytic activity for esterification due to its high acidity and appropriate miscibility with reactants, with an ultrahigh 97.58% conversion of oleic acid under the optimum conditions (i.e. reaction time, 1.8 h; catalyst amount, 3 wt%; alcohol/acid molar ratio, 13:1, temperature 70 °C) acquired from the Box–Behnken response surface methodology. With the novel strategy of multi –SO3H modification on ILs, our catalyst had an approaching or even superior oleic acid conversion rate compared to other reported catalysts with considerably lower catalyst dosage and shorter reaction time. More importantly, it also exhibited high generality for converting various FFA feedstocks into biodiesel with considerable conversion within 93.59–94.33% under a rather lower catalyst dosage, which showed the valuable potential for converting low-cost oils into biodiesel from an economic and environmental perspective.

Establishing an enzyme cascade for one-pot production of \u03b1-olefins from low-cost triglycerides and oils without exogenous H2O2 addition

BackgroundBiological α-olefins can be used as both biofuels and high value-added chemical precursors to lubricants, polymers, and detergents. The prototypic CYP152 peroxygenase family member OleTJE from Jeotgalicoccus sp. ATCC 8456 catalyzes a single-step decarboxylation of free fatty acids (FFAs) to form α-olefins using H2O2 as a cofactor, thus attracting much attention since its discovery. To improve the productivity of α-olefins, significant efforts on protein engineering, electron donor engineering, and metabolic engineering of OleTJE have been made. However, little success has been achieved in obtaining α-olefin high-producer microorganisms due to multiple reasons such as the tight regulation of FFA biosynthesis, the difficulty of manipulating multi-enzyme metabolic network, and the poor catalytic performance of OleTJE.ResultsIn this study, a novel enzyme cascade was developed for one-pot production of α-olefins from low-cost triacylglycerols (TAGs) and natural oils without exogenous H2O2 addition. This artificial biocatalytic route consists of a lipase (CRL, AOL or Lip2) for TAG hydrolysis to produce glycerol and free fatty acids (FFAs), an alditol oxidase (AldO) for H2O2 generation upon glycerol oxidation, and the P450 fatty acid decarboxylase OleTJE for FFA decarboxylation using H2O2 generated in situ. The multi-enzyme system was systematically optimized leading to the production of α-olefins with the conversion rates ranging from 37.2 to 68.5%. Furthermore, a reaction using lyophilized CRL/OleTJE/AldO enzymes at an optimized ratio (5 U/6 μM/30 μM) gave a promising α-olefin yield of 0.53 g/L from 1500 μM (~1 g/L) coconut oil.ConclusionsThe one-pot enzyme cascade was successfully established and applied to prepare high value-added α-olefins from low-cost and renewable TAGs/natural oils. This system is independent of exogenous addition of H2O2, thus not only circumventing the detrimental effect of H2O2 on the stability and activity of involved enzymes, but also lower the overall costs on the TAG-to-olefin transformation. It is anticipated that this biotransformation system will become industrially relevant in the future upon more engineering efforts based on this proof-of-concept work.

Immobilized polymeric sulfonated ionic liquid on core-shell structured Fe3O4/SiO2 composites: A magnetically recyclable catalyst for simultaneous transesterification and esterifications of low-cost oils to biodiesel

In accordance with the need of green and sustainable development, a magnetically recyclable solid catalyst was developed for the transformation of low-cost oils to biodiesel via simultaneous transesterification and esterifications in an efficient and environmentally benign manner. For this aim, the magnetic Fe3O4/SiO2 composites composed of iron oxides as the core and silica as the shell, were prepared, and then polymeric acidic ionic liquid (IL) was immobilized on the magnetic support through radical grafting copolymerization of Brønsted acidic IL, 1-vinyl-3-(3-sulfopropyl)imidazolium hydrogen sulfate, onto the magnetic support. The characterization results showed that the perfect core-shell structured Fe3O4/SiO2 support with good magnetic responsiveness was formed, and the polymeric acidic IL was tethered on the magnetic support. The combination of polymeric acidic IL with magnetic porous nanoparticles could enhance the catalytic activity and favored the separation performance of the catalyst. The solid catalyst exhibited high activities for both transesterification of soybean oil and esterification of free fatty acids generally presented in low-cost oils. Moreover, the catalyst could be simply recovered magnetically and efficiently reutilized for several times without significant loss in its activity, thus allowing its being potentially applicable for green and economic production of biodiesel especially from the low-cost oil feedstocks.

Improved continuous locality preserving projection for quantification of extra virgin olive oil adulteration by using laser-induced fluorescence.

An optimized dimensionality reduction technique is proposed as the improved continuous locality preserving projection (ICLPP), which was developed by modifying and optimizing the weighting functions and weighting factors of the continuous locality preserving projection (CLPP) algorithm. With only one adjustable parameter, this optimized technique not only enhances CLPP's capability of maintaining the continuity of the massive data, but also results in better simplicity and adaptability of the algorithm. In this paper, the performance of ICLPP is validated through quantification analysis of the adulteration of extra virgin olive oil (EVOO) with low-cost oils based on laser-induced fluorescence spectroscopy. Through cross validation and comparative studies, ICLPP, combined with the regression algorithm, is employed to predict and screen adulteration in EVOO, and is found to generally outperform other state-of-the-art dimensionality reduction algorithms, especially for prediction of adulterants at low level (<10%). It is evidenced that the ICLPP-based framework is superior in detecting adulteration by using spectral data.

Immobilization of polyoxometalate-based sulfonated ionic liquids on UiO-66-2COOH metal-organic frameworks for biodiesel production via one-pot transesterification-esterification of acidic vegetable oils

In accordance with the need of green and cleaner production, the aim of the present study is to fabricate an organic-inorganic hybrid recyclable catalyst with both Brönsted and Lewis acid sites for the one-pot production of biodiesel from the low-cost acidic oil feedstocks. To achieve this, the UiO-66-2COOH metal-organic framework materials (MOFs) were firstly functionalized with Keggin-type polyoxometalate (POM) acids through the in-situ preparation strategy, and then the sulfonated acidic ionic liquids (AILs) were further incorporated into the prepared POM/UiO-66-2COOH composites by pairing polyoxometalate anions with functionalized IL cations. The as-prepared AILs/POM/UiO-66-2COOH solid catalyst features a high surface area and an increased acidity, thus combining the merits of Brönsted and Lewis acids together with the heterogeneous microenvironment of MOFs. The solid acid catalysts were fully characterized by several techniques, and the results demonstrated that the polyoxometalate-based sulfonated AILs were virtually immobilized on the UiO-66-2COOH MOFs, and furthermore the porous crystalline structure of the UiO-66-2COOH material was almost unaltered after the immobilization processes. The solid catalyst had excellent catalytic activities toward the simultaneous transesterification and esterification of simulated low-cost oils with long-term stability and good reusability, and moreover still remained considerable activities even with the existence of 9 wt% free fatty acid and 3 wt% water in the low-cost oils. Therefore, this solid catalyst shows potential applications for the one-step biodiesel production especially from the low-cost feedstocks which usually contain high amounts of free fatty acid and water.

Heteropoly acid-encapsulated metal-organic framework as a stable and highly efficient nanocatalyst for esterification reaction.

Metal–organic frameworks (MOFs) have been shown to be promising candidates in the recent decades for the immobilization of guest active species due to their diversified structures, porosity, and high surface area. In this study, silicotungstic acid (HSiW) encapsulated UiO-66 has been successfully synthesized by one-pot synthesis strategy. The synthesized composite (HSiW-UiO-66) was characterized by X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), nitrogen adsorption–desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric (TG) techniques, and the HSiW-UiO-66 was also employed as a solid acidic catalyst for the synthesis of biodiesel by esterification of lauric acid with methanol. The results revealed that the HSiW-UiO-66 composite had better textural properties (such as large BET surface area (758.3 m2 g−1), large pore volume (0.438 cm3 g−1), and smaller particle size (about 50–200 nm)), good thermal stability, and high catalytic activity. In addition, the effect of the esterification process parameters on biodiesel production was analyzed using single factor experimental method combined with response surface methodology (RSM); a high conversion of 80.5% with single factor optimization and 92.8% with RSM was obtained. More importantly, the conversion of lauric acid decreased from 80.5% to just 70.2% when the catalyst had been reused six times, which exhibited that the catalyst had excellent reusability. The high activity of HSiW-UiO-66 benefited from low activation energy of 27.5 kJ mol−1. This work thus offers an underlying application for green biodiesel obtained from free fatty acids esterification or pre-esterification of low-cost oils with high acid value.

Improving Biodiesel Conversions from Blends of High- and Low-Acid-Value Waste Cooking Oils Using Sodium Methoxide as a Catalyst Based on a High Speed Homogenizer

Biodiesel is an environmentally friendly and sustainable fuel. However, the high price of the biodiesel produced from pure vegetable oil contributes to making it uncompetitive in the market. If we can make low cost oils such as waste cooking oil and high-acid-value oil available as resources, the cost of biodiesel production will be reduced significantly. However, these low cost oils cannot be used to produce biodiesel directly because they usually contain a large amount of free fatty acids. They have to undergo a preparatory procedure to lower the acid value to a specific value. The purpose of this study was to lower the amount of free fatty acids in waste cooking oils by blending high- and low-value oils at different ratios and to reduce the transesterification reaction time using a high speed homogenizer, which has the potential to easily enlarge the capacity scale. We used a high-acid-value oil to low-acid-value oil volume ratio of 4:6 as a control. A high conversion rate (97.1%) was achieved under the optimal reaction conditions: methanol-to-oil molar ratio, 9:1; amount of catalyst (CH3ONa) used, 0.75 wt %; reaction temperature, 65 °C; rotation speed, 8000 rpm; and reaction time, 8 min.

Current scenario of catalysts for biodiesel production: a critical review

Abstract Due to increasing concerns about global warming and dwindling oil supplies, the world’s attention is turning to green processes that use sustainable and environmentally friendly feedstock to produce renewable energy such as biofuels. Among them, biodiesel, which is made from nontoxic, biodegradable, renewable sources such as refined and used vegetable oils and animal fats, is a renewable substitute fuel for petroleum diesel fuel. Biodiesel is produced by transesterification in which oil or fat is reacted with short chain alcohol in the presence of a catalyst. The process of transesterification is affected by the mode of reaction, molar ratio of alcohol to oil, type of alcohol, nature and amount of catalysts, reaction time, and temperature. Various studies have been carried out using different oils as the raw material; different alcohols (methanol, ethanol, butanol); different catalysts; notably homogeneous catalysts such as sodium hydroxide, potassium hydroxide, sulfuric acid, and supercritical fluids; or, in some cases, enzymes such as lipases. This article focuses on the application of heterogeneous catalysts for biodiesel production because of their environmental and economic advantages. This review contains a detailed discussion on the advantages and feasibility of catalysts for biodiesel production, which are both environmentally and economically viable as compared to conventional homogeneous catalysts. The classification of catalysts into different categories based on a catalyst’s activity, feasibility, and lifetime is also briefly discussed. Furthermore, recommendations have been made for the most suitable catalyst (bifunctional catalyst) for low-cost oils to valuable biodiesel and the challenges faced by the biodiesel industry with some possible solutions.

Use of ATR-FTIR spectroscopy coupled with chemometrics for the authentication of avocado oil in ternary mixtures with sunflower and soybean oils

ABSTRACTAvocado oil is a high-value and nutraceutical oil whose authentication is very important since the addition of low-cost oils could lower its beneficial properties. Mid-FTIR spectroscopy combined with chemometrics was used to detect and quantify adulteration of avocado oil with sunflower and soybean oils in a ternary mixture. Thirty-seven laboratory-prepared adulterated samples and 20 pure avocado oil samples were evaluated. The adulterated oil amount ranged from 2% to 50% (w/w) in avocado oil. A soft independent modelling class analogy (SIMCA) model was developed to discriminate between pure and adulterated samples. The model showed recognition and rejection rate of 100% and proper classification in external validation. A partial least square (PLS) algorithm was used to estimate the percentage of adulteration. The PLS model showed values of R2 > 0.9961, standard errors of calibration (SEC) in the range of 0.3963–0.7881, standard errors of prediction (SEP estimated) between 0.6483 and 0.9707, and good prediction performances in external validation. The results showed that mid-FTIR spectroscopy could be an accurate and reliable technique for qualitative and quantitative analysis of avocado oil in ternary mixtures.

ChemInform Abstract: Current Status and New Developments of Biodiesel Production Using Fungal Lipases

AbstractReview: 178 refs.

Thermochemical data of the oleic acid esterification reaction: A quantum mechanics approach

Biodiesel is an important renewable fuel that can be obtained from low cost oils once the esterification reaction of free fatty acids is carried out as a pretreatment. Scarcity of reliable thermochemical properties motivated the use of computational calculations to accurately predict these data for biodiesel compounds. The purpose of this study is to calculate thermochemical data of oleic acid esterification reactions with methanol, ethanol and propanol at several temperatures using the B3LYP hybrid functional with the standard 6-311+G(d,p) basis set. Calculated values of enthalpy of formation were corrected by applying a linear regression correction specifically developed for fatty acids and esters in order to decrease systematic errors related to the negligence of high order electron correlation energies in the B3LYP functional. Results showed that, although the esterification reactions are favoured by the temperature increase, these reactions are not spontaneous within the considered temperature range (from 273.15 to 373.15K), which indicates that additional energy is necessary to accomplish them. Methanol is the most reactive alcohol due its higher partial charge values and chemical equilibrium constants. All these values can be useful to supply missing experimental data in the literature and to better understand the thermodynamics of the oleic acid esterification reaction for biodiesel production purpose.

Barcode DNA high‐resolution melting (Bar‐HRM) analysis as a novel close‐tubed and accurate tool for olive oil forensic use

The adulteration of high-priced olive oil with low-cost oils and the fraudulent labelling of oil products make the identification and traceability of vegetable oil species in the food chain very important. This paper describes a high-resolution melting analysis-based method using chloroplast barcoding regions as target (Bar-HRM) to obtain barcoding information for the major vegetable oil species and to quantitatively identify the botanical origin of plant oils. The detection of adulteration of olive oil with canola oil was used as a case study. The proposed method was capable of distinguishing among different vegetable oil species and detecting a level of 1% (w/w) of canola oil in olive oil. Bar-HRM analysis is a more accurate, faster and less costly alternative method to authenticate vegetable oils, including olive oil, and to detect mixtures of oils.

Utilization of soya-based polyol for High solid PU-coating application

Soyabean oil is one of the most abundant and low-cost vegetable oils available in most parts of the world. In presence study, Novel polyester polyols were prepared physically blending from Soya phosphate ester polyol (SOPEP) and Soyabean oil based monoglyceride. High solids polyurethane (PU) coating formulations were developed by reacting novel polyester polyols with aromatic as well as aliphatic isocyanate adducts in different NCO/OH ratios. Structure of polyurethane resins was confirmed by FT-IR spectroscopy. The polyurethane resins were coated on test panels and tested for their flexibility, scratch hardness, cross-hatch adhesion, impact hardness, pencil hardness and solvent resistance as per standards. Thermal stability of these polymers was determined by thermogravimetric analysis (TGA).

Transesterification of soybean oil over WO3 supported on AlPO4 as a solid acid catalyst

WO3/AlPO4 catalysts were prepared by impregnation of AlPO4 with ammonium metatungstate. Powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and thermo gravimetric and differential thermal analysis (TG–DTA) demonstrated that the tungsten compound was incorporated into AlPO4 forming the catalyst with an enhanced acidity. When transesterification of soybean oil over the catalysts was performed, the catalyst with 30wt.% WO3 loading and calcined at 1073K, exhibited the best catalytic activity with a conversion of 72.5%. The transesterification was optimal at 453K for 5h with a methanol/oil ratio of 30:1 and catalyst dosage of 5wt.%. Free fatty acid (FFA) and water did not affect the catalytic activity. The catalyst proved to be stable over four transesterification cycles as it lost only 4% of its activity after being reused four times. The catalyst could be used for the transesterification of low-cost oils for biodiesel production.

Promoting calorimetry for olive oil authentication

The aim of this paper is to promote calorimetry for olive oil authentication. It is our belief that the melting and freezing curves by DSC of olive oil and other edible oils could be correlated with quality, origin and storage history of the oil in a simple way, suitable for oil industry and market. Nucleation, crystallization kinetics and transition enthalpies of oil are indeed strongly dependent on molecular interactions, that is any change of oil acidic composition and minor components can be detected, as we have recently demonstrated. In particular, addition of low-cost oils to extra virgin olive oil (EVOO) and thermal and/or mechanical treatments (refinement, deodorization, filtration, etc.) of EVOO can be assessed by a first-sight analysis of the thermograms. Protocols to obtain reproducible DSC thermograms and experiments to understand the origin of the often-observed non-reproducibility, which prevented until now the use of calorimetry for oil authentication, are here described. An explanation of the melting curves even limited to the main features is a hard task owing to the polymorphism of the numerous triacylglycerols (TAG), the main component of the oil, the complexity of their mutual interactions and the effects of the minority components. To outline the level of this challenge we report: (i) the evidence that thermodynamic and kinetic processes overlap during heating of solid EVOOs and (ii) the melting curve of one pure TAG with its polymorphic transitions.

COMPARISON OF ENGINE PERFORMANCE AND EMISSIONS FOR PETROLEUM DIESEL FUEL, YELLOW GREASE BIODIESEL, AND SOYBEAN OIL BIODIESEL

Biodiesel is a nontoxic, biodegradable and renewable alternative fuel that can be used with little or no enginemodifications. Biodiesel is currently expensive but would be more cost effective if it could be produced from lowcost oils(restaurant waste, frying oils, animal fats). These lowcost feedstocks are more challenging to process because they containhigh levels of free fatty acids. A process for converting these feedstocks to fuelgrade biodiesel has been developed anddescribed previously. The objective of this study was to investigate the effect of the biodiesel produced from high free fattyacid feedstocks on engine performance and emissions. Two different biodiesels were prepared from animal fatbased yellowgrease with 9% free fatty acids and from soybean oil. The neat fuels and their 20% blends with No. 2 diesel fuel were studiedat steadystate engine operating conditions in a fourcylinder turbocharged diesel engine. Although both biodiesel fuelsprovided significant reductions in particulates, carbon monoxide, and unburned hydrocarbons, the oxides of nitrogenincreased by 11% and 13% for the yellow grease methyl ester and soybean oil methyl ester, respectively. The conversion ofthe biodiesel fuels energy to work was equal to that from diesel fuel.