Rapeseed Oil Fatty Acids Research Articles

Formation of lipid-derived volatile products through lipoxygenase (LOX)- and hydroperoxide lyase (HPL)- mediated pathway in oat, barley and soy bean

The aim of this study was to explore the formation of volatile lipid oxidation products by the lipoxygenase (LOX)-hydroperoxide lyase (HPL)-mediated pathway in oat, barley and soy bean. LOX activity was found only in barley and soy bean samples, but the lipase and HPL activity was detected in all samples. HPL showed particularly high activity with 13-hydroperoxides, while the activity was quite low when using 9-hydroperoxides, especially in the oat and barley. The optimum pH for HPL in different samples was similar, i.e., pH 6–7. In this condition, the volatile compounds formed dramatically with aldehydes and furans as the dominant products. Furthermore, a remarkable enzymatic degradation of lipids occurred during the preparation of food models with highly refined rapeseed oil (RO) and rapeseed oil fatty acid (ROFA) emulsions, where the ROFAs were more prone to oxidation than RO. This study shows the significance of lipid-degrading enzymes in plant-food flavour formation.

The Physicochemical Basis for the Production of Rapeseed Oil Fatty Acid Esters in a Plug Flow Reactor

This article describes the results of a comprehensive comparative study of the production of fatty acid ethyl esters (FAEEs) for use as biodiesel in perfect mixing reactors (PMRs) and plug flow reactors (PFRs). The products obtained on a laboratory scale at all stages of the separation and purification of the FAEE phase were analyzed using the FTIR, XRF and GC-MS methods. We compared distillation methods for the separation of stoichiometrically excessive ethanol from the reaction mixture. Neutralization methods with H2SO4 solution and carbonation with CO2 were applied for FAEE phase purification from the catalyst. Emulsions formed during the water flushing stage were analyzed via the optical microscopy method. The optimal conditions of stirring speed and temperature were selected to maintain a high level of FAEE–water phase contact area with minimum phase separation time. The efficiency of the carbonation method for catalyst neutralization in the FAEE phase has been proven, allowing us to consider this method as an alternative to the traditional acid neutralization method. According to the results of experimental studies, we have developed a new high-performance technological scheme for the production of fatty acid esters in PFRs. The synthesis of FAEEs in a stoichiometric excess of ethanol of about 1:50 allowed us to increase the reaction rate and productivity of the synthesis unit after the transition from a PMR to a PFR. The yield of the product amounted to 86.7%. The purified FAEE fraction complied with most EN14214 specifications.

A new type of mixed vegetable insulating oil with better kinematic viscosity and oxidation stability

• The molecular dynamics model of mixed vegetable insulating oil with different proportion was established. • The effects of different mixing ratios on the kinematic viscosity of mixed oil were studied by molecular dynamics. • The difference of oxidation stability between palm fatty acid ester and rapeseed oil was studied by First-Principle. • A mixing ratio with good kinematic viscosity and oxidation stability was obtained. Natural ester is a new type of environment-friendly energy, and the research on its performance is crucial in order to be widely popularized and applied in electrical equipment. The mixing of different natural esters can ameliorate the performance handicap of natural esters. Therefore, two widely applied natural esters, rapeseed oil and palm fatty acid ester (PFAE) were selected in this paper. The kinematic viscosity and oxidation stability of mixed oil were analyzed on the basis of the establishment of the mixture of two oils with different mixing proportion by simulation. Results indicate that the kinematic viscosity of the mixed oil decreased with the addition of PFAE. The kinematic viscosity of the mixed oil decreased by 51.3% when the mixing ratio was 80% rapeseed oil and 20% PFAE. The addition of short chain oil molecules increases the mean square displacement, mean-square radius of gyration and free volume of the mixed oil. The oil molecules in the mixed system have fewer tangles and reduced internal friction between them. DFT calculation shows that numerous electron traps in PFAE provide a channel for the transition of valence electrons. The methyl group in PFAE has strong positive electrostatic potential and strong electron affinity, which makes the oxidation stability of PFAE lower than that of rapeseed oil. Therefore, 80% rapeseed oil and 20% PFAE are the best mixing ratio in this study. This ratio has the best improvement on the kinematic viscosity of the mixed oil and the least influence on the oxidation stability.

Effective Epoxidation of Fatty Acid Methyl Esters with Hydrogen Peroxide by the Catalytic System H3PW12O40/Quaternary Phosphonium Salts

Six quaternary phosphonium salts (QPSs) in combination with phosphotungstic heteropolyacid, H3PW12O40, were tested in the epoxidation of rapeseed oil fatty acid methyl esters with a hydrogen peroxide aqueous solution. The QPSs consisted of trihexyl(tetradecyl)phosphonium [P6], tributyl-tetradecylphosphonium [P4] or tetraoctylphosphonium [P8] cation and different anions—chloride (Cl−), bromide (Br−), tetrafluoroborate (BF4−), bis(trifluoromethylsulfonyl)amide (NTf2−), bis(2,4,4-trimethyl-pentyl)phosphinate (Phosf−). The influence of the kind of QPS and temperature on the epoxy number, iodine number, glycol content has been determined. The epoxidation was confirmed using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and elemental analysis CHO. Two QPSs with a trihexyltetradecyphosphonium cation—[P6][Fosf] and [P6][Cl]—were selected as the most effective in the studied epoxidation process. The proposed kinetic model takes into consideration the two reactions, namely, epoxidation and epoxy ring opening involving the formation of hydroxyl groups. The rate constants and activation energies for epoxidation fatty acid methyl esters were determined.

Testing of lubricating properties of mixtures of diesel and RME biofuels with the addition of linoleic acid

In connection with the limited resources of fossil fuels and the reduction of emissions and stimulation of agricultural areas, a very important indication is the search for alternative fuels – biofuels. The article presents the results of testing the lubricating properties of selected fuel mixtures. The lubricity of diesel fuel (DF), DF with 7% content of methyl esters of rapeseed oil fatty acids (RME), technical linoleic acid and DF with 7% content of RME and 10% content of technical linoleic acid was tested. The research was carried out on the author's research stand in the amount of 20 dm3 of mixture. Four parameters were taken into account: mass loss of samples, the footprint area of cooperation, diameter of equivalent wheel and average value of the coefficient of friction. It has been shown that the addition of linoleic acid to diesel fuel containing RME causes a significant increase in the mass loss of the samples and the footprint area of cooperation as well as its diameter of equivalent wheel, during lubrication with such a mixture. As a result of the addition of linoleic acid, no positive results were obtained, as the lubricating properties in this case deteriorated. Therefore, it is justified to continue looking for fuel additives that will eliminate this negative effect.

Biodiesel production from rapeseed oil and low free fatty acid waste cooking oil using a cesium modified natural phosphate catalyst.

The present study focuses on the catalytic activity of cesium modified natural phosphate in biodiesel production from rapeseed oil and low free fatty acids (FFA) used in cooking oil. The catalyst was prepared by impregnation of cesium chloride (CsCl) on the natural phosphate followed by calcination up to 800 °C. The phosphate based catalyst was thermally, structurally, morphologically, and texturally characterized in order to determinate the relationship between its physicochemical properties and its catalytic activity. The chosen catalyst was demonstrated to be an active catalyst for the transesterification of rapeseed oil achieving a biodiesel yield of 99.55% under suitable reaction conditions: a methanol to oil molar ratio of 12 : 1, reaction temperature of 70 °C, catalyst amount of 4 wt% based on oil weight and reaction time of 6 h. Results from low FFA waste cooking oil transesterification indicated that a methyl esters yield of 99.52% could be obtained. Furthermore, results from esterification/transesterification of acidified rapeseed oil indicate that a yield of 93% may be obtained, thus giving rise to a potential application in 2nd generation biodiesel production from low acidic oils. Some important physicochemical properties of the obtained biodiesel were evaluated and compared with the EN14214 and ASTM D-6751 standards for biodiesel specifications.

Evaluation of Ethoxylated Rapeseed Oil Fatty Acids Methyl Esters as Nonionic Co-Surfactants in Hand Dishwashing Liquids

Abstract The effect of ethoxylated rapeseed oil fatty acid methyl esters (ROFAME) on the viscosity, functional properties and skin compatibility of hand dishwashing liquids was analyzed. It was found that, over the test range, both the degree of ethoxylation and concentration in the formulation were essential for the properties of the evaluated products. Among others, this was due to the fact that ROFAME had the favorable effect of modifying the viscosity of these formulations to an acceptable range. The relationship between the concentration and degree of polyaddition of ROFAME on the detergent and foaming properties of the complete formulation was presented, showing their increase in comparison to the reference dishwashing liquid without ROFAME. With respect to the parameters relating to the skin irritant, the degree of skin dryness after dishwashing with the auxiliary surfactants was lower.

Branched-chain dicationic ionic liquids for fatty acid methyl ester assessment by gas chromatography.

Twelve bis- or dicationic ionic liquids (ILs) including eight based on imidazolium, a single one based on phosphonium, and three based on pyrrolidinium cationic units were prepared with the bis(trifluoromethyl sulfonyl) imide anion. The two identical cationic moieties were attached by different alkyl spacers having three or five carbons and differing alkyl substituents attached to the spacer. The SLB-IL111 column, as the most polar commercial stationary phase known, was included in the study for comparison. Isothermal separations of a rapeseed oil fatty acid methyl ester (FAME) sample were used to study and compare the 12 IL-based column performances and selectivities. The retention times of the most retained methyl esters of lignoceric (C24:0) and erucic (C22:1) acids were used to estimate the IL polarity. The phosphonium dicationic IL column was, by far, the least polar. Imidazolium-based dicationic IL columns were the most polar. Polarity and selectivity for the FAME separation were somewhat related. The separation of a 37-FAME standard mixture allowed the investigation of selectivity variations observed on the 12 IL-based columns under temperature gradients up to 230°C. The remarkable selectivity of the IL-based columns is demonstrated by the detailed analysis of the cis/trans C18:1 isomers of a partially hydrogenated vegetable oil sample on 30-m columns, separations competing with that done following an "official method" performed on a 100-m column. Graphical abstract Separation of fatty acid methyl esters on a 30-m 3m2C5(mpy)2. 2NTf2 branched-chain dicationic IL-based column. Branched chain dicationic ILs show great selectivity for separation of cis/trans, ω-3/ω-6, and detailed analysis of cis/trans fats.

Evaluation of biodegradability and stability of biodiesel fuel and its mixtures

Global warming has forced humanity to care for greenhouse gas emission reductions, at the same time the production and use of biofuels. One of the positive environmental properties of biofuels is fast biological degradation. Biological degradability of pure rapeseed oil fatty acid butyl esters (RBE) within 28 days is 70% and such product meets the requirements for biofuel. During the same period, only 26% of mineral diesel fuel (D) is decomposed. Multi-component fuel containing up to 30% biofuel is less biodegradable and specified as a partially biodegradable material. The peroxide and acid number of pure biodiesel is growing rapidly when aging compared to that of mineral diesel and multicomponent fuel mixtures. The acid number of pure rapeseed oil fatty acid methyl esters (RME) was higher than the standard requirements after 3 weeks of storage. The acid number of mixtures containing 15% RME (RME15B15D70) and RBE (RBE15B15D70 and RBE25B25D50) was less than 0.5 mg KOH/g–1 after 8 weeks of storage. Multi-component fuel is more resistant to oxidation than pure biodiesel fuel.

Rapeseed Oil as Feedstock for High Functionality Polyol Synthesis

In this study, polyols with high average functionality were synthesized from a renewable resource, rapeseed oil, as raw material for rigid PU foam production. A well-known method of rapeseed oil fatty acid double bond epoxidation was used to introduce oxirane rings into rapeseed oil structure. The temperature influence on epoxidation reaction conversion rate was studied by volumetric and FTIR spectra analysis. After epoxidation of rapeseed oil, an oxirane ring-opening reaction was carried out to obtain high functionality polyols. Diethylene glycol, a conventional oxirane ring-opening reagent, was compared to amine-based polyfunctional alcohols, diethanolamine and triethanolamine. The introduction of tertiary amine groups into the polyol structure provided catalytical properties for obtained polyols, which will allow a reduction of the amount of catalysts in polyurethane foam formulations. Hydroxyl value, acid value, moisture content, viscosity and density of synthesized polyols were determined, and their structure and average functionality were analyzed by FTIR and MALDI-TOF spectroscopy and GPC analysis. Also, the main characteristics of rigid PU foam obtained from synthesized polyols were determined.

Feeding of palm oil fatty acids or rapeseed oil throughout lactation: Effects on energy status, body composition, and milk production in Norwegian dairy goats

The objective of this experiment was to examine how supplements of rapeseed oil or palm oil fatty acids would affect milk production and composition, body lipid stores, and energy balance in 30 multiparous goats of Norwegian dairy goat breed. The experiment lasted 230 d, with 1 to 120 d in milk (DIM) for indoor feeding (P1), 120 to 200 DIM for mountain grazing (P2), and 200 to 230 DIM for indoor feeding (P3). Grass silage was fed according to appetite during indoor feeding periods. After an adjustment period (1-60 DIM) when the control diet was given to the goats, the animals were subdivided into 3 groups of 10 goats. Treatments (60-230 DIM) were (1) basal concentrate (control; no added fat); (2) control concentrate with 8% (added on air-dry basis) hydrogenated palm oil enriched with palmitic acid (POFA); and (3) control concentrate with 8% (added on air-dry basis) rapeseed oil (RSO). Individual energy balances based on energy intake and milk production were estimated on 10, 30, 60, 90, 120, 200, and 230 DIM. At the same times, body weight (BW), body condition score (BCS), body mass index, and body tissue stores using computed tomography were monitored. Silage intake was depressed by POFA throughout the experimental period. Reduced BW and body mass index were observed in the POFA and RSO groups, whereas no effect on BCS or body composition was observed throughout lactation. Generally, a minor decrease in BW was observed from 10 to 120 DIM (only 0.6 kg on average) and the total amount of body lipid was reduced by 4.4 kg. During the mountain grazing period, a further reduction in body lipid stores (2.7 kg) was observed, and BW was reduced by 3.9 kg in the same period. The goats mobilized, on average, 72% of their fat reserves during the first 200 DIM. In this period, dietary fat supplementation did not reduce the mobilization of adipose tissue but resulted in greater milk fat yield (2 kg more, on average, compared with the control group). Milk yield was not affected by POFA or RSO supplementation. Milk fat content was higher in the POFA group than in the control and RSO groups. Milk protein and lactose contents were not affected by lipid supplements. In late lactation, a rapid accumulation of fat deposits followed the intense mobilization during the grazing period. Dietary lipid supplements had no effect on milk fat yield at this stage. Milk production depends heavily on the ability to mobilize body lipid stores, and neither POFA nor RSO supplements at rates used in our study affected this mobilization.

Conversion of triglycerides to fuel hydrocarbons over a Pt–Pd–Al–HMS catalyst

The hydroconversion of rapeseed oil fatty acid triglycerides (TGs) over a mesoporous platinum–palladium aluminosilicate catalyst has been studied. It has been shown that, in a temperature range of 250–375°C at a hydrogen pressure of 60 atm, the TGs undergo complete deoxygenation and the resulting products undergo isomerization. Under optimum process conditions, the diesel fraction yield is 94%. The resulting fraction can be used as an environmentally safe fuel component.

Evolution of active ingredients and catalytic properties of Pt-Sn/Al2O3 catalysts in the selective deoxygenation reaction of vegetable oils

The evolution of the structure of Pt–Sn/Al2O3 catalysts and their catalytic properties in the reaction of the reductive deoxygenation of rapeseed oil fatty acid triglycerides (FATGs) have been studied. The catalysts were prepared by deposition from an organic solution of a mixture of platinum and tin compounds, as well as a heterometallic (PPh4)3[Pt(SnCl3)5] complex, in which platinum and tin atoms are linked by a metal–metal bond. It has been shown that the use of the heterometallic complex as a precursor with a tin to platinum molar ratio of 5 results in the formation of clusters of nanosized tin (2+; 4+) oxides and particles of a metastable PtSn3 ± δ alloy on the surface of the catalyst after reductive activation. In the presence of this catalyst, the exhaustive conversion of the feed FATGs and the selectivity for hydrocarbons above 98% have been achieved. The gaseous products CO, CO2, and CH4 are formed in trace quantities. The results show that the deoxygenation occurs not via the known decarboxylation and decarbonylation route, but also through the step of the selective reduction of oxygen and almost complete suppression of cracking of the organic moieties of FATGs.

Esterification of rapeseed oil fatty acids using a carbon-based heterogeneous acid catalyst derived from cellulose

The present work demonstrates a single-step preparation of sulfo carbon-based solid acid catalyst (CSO3H) obtained from cellulose by direct carbonization–sulfonation with conc. H2SO4. The variation of reaction conditions, such as, reaction temperature (50–180°C), weight ratio of H2SO4 to cellulose (5/1–30/1) and reaction time (1–10h) provided CSO3H with relatively abundant density of acid sites attached on catalyst surface. The CSO3H with the highest density of SO3H groups (0.81mmol H+/g) was obtained at 100°C using weight ratio of H2SO4 to cellulose (20/1) after 3h of reaction. The catalyst was characterized by means of N2 sorption analysis (average pore diameter 12.8nm, specific surface area 1.38m2/g, pore volume 0.004cm3/g), FT-IR, TG, XRD, FE-SEM and S elemental analysis. The conversion of rapeseed oil fatty acids (RFA) in esterification reactions with CSO3H as catalyst was quite similar to the commercial Amberlyst-15 and the biodiesel with ester content of ≥96.5% was successfully obtained under optimized reaction conditions.

Synthesis and lubricating properties of neopentyl glycol oligoesters based on rapeseed oil

Purpose – The aim of this work is to synthesize neopentyl glycol oligoesters based on adipic acid and rapeseed oil (NOAR) which may be used as the renewable and environmentally acceptable base fluids to replace mineral oils in the future. Design/methodology/approach – Oligomeric intermediates were synthesized in the first esterification of neopentyl glycol with adipic acid and characterized by Gas Chromatography-Mass Spectrometer (GC-MS) to calculate the average oligomerisation degree. NOAR were synthesized in the second esterification of oligomeric intermediates with rapeseed oil fatty acid. The effects of average oligomerisation degree on the viscosity, viscosity index, pour point, oxidative stability and biodegradability of NOAR were investigated; the tribological properties and thermal stability of NOAR were evaluated by four-ball tribometer and TGA, respectively. Findings – Results show that with the increase of average oligomerisation degree from 2.10 to 4.34, the viscosity of NOAR increased from 101.1 to 182.0 (mm2/s) at 40°C and 18.3 to 30.1 (mm2/s) at 100°, respectively, and their oxidation stability can be improved as well. The yields of NOAR were 83.3-89.4 per cent, and the evaluated properties were as follows: viscosity index of over 200, pour point of below −43°C, biodegradation rate of more than 96 per cent, maximum non-seizure load (PB value) of 784 N, wear scar diameters of 0.40 mm and thermal decomposition temperature of higher than 300°C. Originality/value – This work provides a method to synthesize rapeseed oil-based oligoesters which can serve as the renewable and environmentally acceptable base fluids with tunable viscosity by controlling the oligomerisation degree of esterification.

Synthesis of activated carbon based heterogenous acid catalyst for biodiesel preparation

The present work illustrates the synthesis of 4-sulfophenyl activated carbon based solid acid catalyst (ACPhSO3H), obtained from activated carbon (AC) by arylation with 4-sulfobenzenediazonium chloride. The variation of reaction conditions, such as, reaction temperature (20–85°C) and weight ratio of sulfanilic acid (precursor of 4-sulfobenzenediazonium chloride) to AC (0.14/1–14.00/1) provided ACPhSO3H with relatively high density of acid sites. The ACPhSO3H with the highest PhSO3H density (0.72mmol H+/g) was obtained using weight ratio of sulfanilic acid to AC (7.00/1) at 70°C after 10min. The catalyst was characterized by means of nitrogen adsorption analysis (average pore diameter 10.1nm, specific surface area 114m2/g, pore volume 0.29cm3/g), FT-IR, TG, XRD, FE-SEM and S elemental analysis. The spent catalyst can be easily regenerated recovering its initial density of acid sites. Upon employment in esterification reactions of rapeseed oil fatty acids, ACPhSO3H showed similar catalytic performance to Amberlyst-15.

Properties of rapeseed oil fatty acid alkyl esters derived from different alcohols

One of the ways to improve the cold flow properties of biodiesel is to derive it from other alcohols instead of methanol. In this research a three step synthesis of fatty acid alkyl esters (FAAE) in the presence of sulfuric acid was performed via transesterification of rapeseed oil using 11 different linear or branched alcohols (C1C6) – methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, 2-methylbutan-1-ol, pentan-1-ol, 2,2-dimethylpropan-1-ol, 4-methylpentan-2-ol. Furthermore, a vacuum distillation was carried out to increase ester content over ⩾96.5wt.%. It was concluded that an increase of the length of FAAE hydrocarbon chain in alcohol moiety significantly helps to improve the cold flow properties of FAAE distillates. From linear alcohols the minimal values of (cold filter plugging point (CFPP) −17°C, cloud point (CP) −16°C and pour point (PP) −18°C were reached using FAAE derived from butan-1-ol. From branched alcohols the lowest CFPP −24°C, CP −28°C and PP −37°C were achieved by obtaining FAAE from 4-methylpentan-2-ol.

Winter Oilseed Rape Productivity and Nutritional Quality Responses to Zinc Fertilization

Soil Zn is always potentially deficient in Yangtze River Basin (YRB) of China, due to widespread alkaline soils, high soil P, and large Zn removal of high‐yielding oilseed rape (Brassica napus L.) and rice (Oryza sativa L.) cultivars. However, Zn fertilizer response of winter oilseed rape in YRB is not clear. Therefore, on‐farm experiments were conducted at six locations to investigate the effects of experimental sites and Zn rates (0 and 6.8 kg Zn ha−1) on plant growth, seed yield and quality, and Zn uptake of oilseed rape (Huashuang no. 5 cultivar). Across all the sites, Zn application increased seed yield by 5.0 to 16.0%, oil yield by 6.2 to 19.5%, and protein yield by 2.3 to 17.7%. Application of Zn fertilizer increased the concentrations of total oil, oleic acid, and linoleic acid in rapeseed, but reduced stearic acid concentration. No differences were observed on protein and linolenic acid concentrations between Zn rates. Total Zn uptake in plants increased by 13.5 to 62.3% with Zn fertilizer applied, while Zn harvest index reduced by 3.4 to 18.5%. Oilseed rape performance varied among sites. The extensive significant Zn × site interactions indicated that Zn response was dependent on the environments we studied. Thus, Zn fertilizer management will probably need to be adjusted at different sites. Our results suggested to apply Zn fertilizer to improve oilseed rape productivity, nutritional quality, and Zn uptake. This study also increased the understanding of the positive effects of Zn on rapeseed oil content and fatty acids composition.

Kinetics of the hydrotreatment of rapeseed oil fatty acid triglycerides under mild conditions

To establish principal regularities of the hydrotreatment of rapeseed oil fatty acid triglycerides (FATs), the kinetics of this process has been studied at temperatures of 300–380°C, contact times of 0.38–0.10 h, and a hydrogen pressure of 1.0 MPa in a flow fixed-bed reactor. The process is performed over nonsulfided nickel catalysts, which are of great practical interest for the production of green diesel. The kinetic scheme of the process with consideration for target products (alkanes) and all oxygen-containing by-products has been proposed. The quantitative estimate, which enables the prediction of the composition of products for other process conditions, has been obtained for the principal paths of the hydrotreatment of rapeseed oil FATs.

Fuel Impact on the Response of AD3.152 UR Engine

The paper presents results of investigations into the AD3.152 UR engine running on five fuels: commercial diesel oil DO, rapeseed oil fatty acid methyl esters FAME and their blends B10 (90% DO + 10% FAME), B20 (80% DO + 20% FAME), B30 (70% DO + 30% FAME). During the tests, the engine operated in accordance with the full load characteristics. Those characteristics were used to determine the engine response. The paper provides an assessment of the impact of the type of plant-derived fuel on the engine response.