Partial separation of polyunsaturated fatty acid esters from FAMEs mixtures by adsorption on silver nitrate-impregnated silica gel

Mixtures of FAMEs derived from soybean and canola oils were fractionated by contacting their hexane solutions with AgNO₃/SiO₂ adsorbents. Methyl linolenate (18∶3) adsorbed most strongly, followed by methyl linoleate (18∶2), on the AgNO₃/SiO₂. Conditions of the extractions (AgNO₃ loading, amount of adsorbent, methyl soyate/hexane solution concentration, use of successive extractions, and methods of adsorbent regeneration) were varied. Under optimal conditions, the 7.0% of 18∶3 in methyl soyate could be reduced to 0.1%. The described process is a simple method for separating a FAMEs mixture into a fraction that is depleted in polyunsaturated FAMEs and one that is enriched.     

Biotransformation of 2-Benzoxazolinone to 2-Amino-(3<Emphasis Type="Italic">H</Emphasis>)-Phenoxazin-3-one and 2-Acetylamino-(3<Emphasis Type="Italic">H</Emphasis>)-Phenoxazin-3-one in Soil

An alternative to the use of synthetic pesticides is to exploit the natural defense chemicals produced by cereals. An important class of allelochemicals is cyclic hydroxamic acids and related benzoxazolinones. A prolonged degradation experiment of the allelochemical compound from rye 2-benzoxazolinone (BOA) was carried out for up to 90 d at 15°C at three different concentration levels, 3, 3000, and 30,000 nmol BOA· g soil^–1, respectively, in a sandy loam soil. Two main degradation products, 2-amino-(3H)-phenoxazin-3-one (APO) and 2-acetylamino-(3H)-phenoxazin-3-one (AAPO), were identified and quantified by LC-ESI-MS-MS. The half-life of BOA increased with higher levels of BOA added to the soil. Half-lives of BOA, APO, and AAPO were determined by fitting a single first-order model to the degradation data. Half-life of BOA was determined to be 0.6 d in the 3 nmol BOA g soil^–1 treatment. Half-lives of BOA, APO, and AAPO were 3.1, 2.7, and 2.1 d, respectively, in the 3000 nmol BOA· g soil^–1 treatment. In the 30,000 nmol BOA· g soil^–1 treatment, the half-lives were 31 d for BOA and 45 d for APO. The microbial community structure was not affected by addition of BOA to the soil as investigated by analysis of signature fatty acids. The results suggest that the exploitability of BOA for crop protection is dependent on the existing concentration of BOA in the soil and the timing of incorporation of hydroxamic acid synthesizing crops into the soil.     

Efficient solvent-less separation of lipids from municipal wet sewage scum and their sustainable conversion into biodiesel

A very efficient separation of lipids from wet sewage scum was optimised and positively tested on samples taken from several wastewater treatment plants (WWTPs). By simply heating sewage scum at 353 K and centrifuging the heated mass at 4000 rpm per 1 min, a recoverability of 93–99% of total oils was always obtained. This procedure resulted to be effective on samples with very different starting water contents. In all cases, extracted lipids have a very similar composition in terms of free fatty acids (FFAs), calcium soaps (32–40%wt) and glycerides (mono-, di- and tri-glycerides were practically absents), as well as fatty acid profiles. Once separated, lipids were converted into biodiesel through a direct esterification process carried out by adopting three sequential batch reactors, in which methanol and catalysts were charged in counter current. In this way, the complete conversion (>99%) of starting FFAs into FAMEs was perfectly matched with using the minimum amount of reactants under very mild conditions (345 K, 2 h). The overall convenience of the process was completed by the anaerobic digestion of fibrous residues obtained from centrifugation of starting sewage scum: the final biogas resulted largely enough to sustain the heat of process.     

Growth of microalgae using CO2 enriched air for biodiesel production in supercritical CO2

The optimum conditions for lipids productivity and CO₂ fixation of two freshwater strains, namely Chlorella sp. and Pseudochlorococcum sp. and a marine strain; namely Nannochlorpsis sp. have been determined in this work. The species were grown autotrophically under aeration with different CO₂ concentrations, ranging from 0.04 to 2% (v/v). The growth was tested in nitrogen sufficient and deficient media at different salinities (0.49–680 mM) and temperatures of 27 and 31 °C. The optimum CO₂ enrichment was found to be 1% (v/v) in both media. Nitrogen starvation resulted in an increase in lipid contents, but at lower growth rate, which resulted in a lower overall lipid productivity. The experimental data were used to determine the kinetic parameters of Haldane model. The Chlorella sp. grew well at salinity levels of up to 460 mM. The highest CO₂ biofixation rate was observed when Chlorella sp. was grown at 27 °C in seawater (230 mM NaCl).Lipids were extracted from harvested marine strain, Nannochlorpsis sp., and enzymatically transesterified to produce biodiesel in supercritical CO₂ (SC–CO₂) medium. It was found that the conversion of biodiesel produced from microalgae lipids was 35% higher than that achieved using lamb fat in a similar system.     

Kinetics of the pre-treatment of used cooking oil using Novozyme 435 for biodiesel production

The pre-treatment of used cooking oil (UCO) for the preparation of biodiesel has been investigated using Novozyme 435, Candida antarctica Lipase B immobilised on acrylic resin, as the catalyst. The reactions in UCO were carried out using a jacketed batch reactor with a reflux condenser. The liquid chromatography–mass spectrometry (LC–MS) method was developed to monitor the mono-, di- and triglyceride concentrations and it was found that the method was sensitive enough to separate isomers, including diglyceride isomers. It was found that the 1,3 diglyceride isomer reacted more readily than the 1,2 isomer indicating stereoselectivity of the catalyst. This work showed that Novozyme 435 will catalyse the esterification of free fatty acids (FFAs) and the transesterification of mono- and diglycerides typically found in UCO when Novozyme 435 is used to catalyse the pre-treatment of UCO for the formation of biodiesel. A kinetic model was used to investigate the mechanism and indicated that the reaction progressed with the sequential hydrolysis esterification reactions in parallel with transesterification.     

Hydrothermal gasification of pure and crude glycerol in supercritical water: A comparative study

A comparative gasification study between pure glycerol and two different kinds of crude glycerol is conducted in supercritical water under various operating parameters to investigate the effect of different compositions in crude glycerol on the gasification behaviors. Among various types of impurities in the crude glycerol, fatty acid methyl esters (FAMEs) exhibit a negative effect on the gas yield and gasification efficiency of crude glycerol in a batch apparatus due to the enhanced tar/char formation. At 650 °C and 5 wt%, gasification in a continuous apparatus exhibits H₂ yields of 26.44 and 35.85 mmol/g feed in 1 min for both types of crude glycerol, which could not be achieved by the batch system even with the reaction time extended up to 120 min. A shorter duration in the non-supercritical state may be the dominant parameter that leads to complete conversion of FAMEs and total gasification of crude glycerol using the continuous system.     

TRANSESTERIFICATION OF PALM OIL AT NEAR-CRITICAL CONDITIONS USING SULFONATED CARBON-BASED ACID CATALYST

This study aims to investigate the production of biodiesel by transesterification of purified palm oil (PPO) at near-critical conditions using a carbon-based catalyst, synthesized by incomplete carbonization of naphthalene in sulfuric acid. The catalyst shows good activity for the reaction; with the most suitable condition found to be at a methanol-to-PPO molar ratio of 12:1, a carbon-based catalyst-to-PPO mass ratio of 0.5 wt.%, a reaction time of 30 min, and a reaction temperature of 270°C. This resulted in a FAME yield of about 95%. However, FAME yields were found to decrease after each reaction cycle from around 95% in the first to 61% in the second cycle, and to only 45% in the third cycle, as a result of catalyst deactivation due to acid leaching.     

应用脂肪酸甲酯快速筛选植物油中掺假地沟油

根据植物油和地沟油中脂肪酸酯存在方式的不同,建立植物油中地沟油掺假的快速筛选方法。植物油中脂肪酸是以甘油三酯的形式存在,地沟油中脂肪酸以脂肪酸甲酯的形式存在,利用气相色谱-质谱的全扫描模式,结合NIST 05标准谱库检索功能,对37 种脂肪酸甲酯进行测定。样品采用直接稀释-气相色谱-质谱全扫描分析脂肪酸甲酯,100 个植物油样品中均未检出脂肪酸甲酯;20 个地沟油样品中13 个检出肉豆蔻酸甲酯（C14∶0）、棕榈酸甲酯（C16∶0）和硬脂酸甲酯（C18∶0）等14 种脂肪酸甲酯,检出率为65%,且70%的检出脂肪酸甲酯的地沟油样品中脂肪酸甲酯种类多、含量较高。因此,若植物油样品脂肪酸甲酯种类多、含量高,则可判定为有地沟油掺假;若脂肪酸甲酯含量低或没有脂肪酸甲酯,则可以进一步用其他指标和方法进行检测,脂肪酸甲酯的检测方法可以作为地沟油掺假的快速粗筛方法。