Cleavage of Carboxylic Acid Moieties in Triacylglycerides During Non‐Catalytic Pyrolysis

Noncatalytic pyrolysis of triacylglyceride (TG) oils is an attractive option for production of renewable fuels and chemicals. This process produces 20–30 wt% of C₂–C₁₀ fatty acids due to the presence of carboxyl moieties in TG. To decipher this process’ mechanism, several compositionally distinct crop oil feedstocks with varied abundances of C₁₈ saturated and unsaturated TG carboxylic acid chains were pyrolyzed for short residence times in a laboratory‐scale continuous turbulent flow reactor. A comprehensive gas chromatographic analysis of the oxygenated products revealed the selective formation of linear saturated monocarboxylic acids (LSMCA) of less than C₁₁ in size, with a specific homological pattern featuring peaks for C₂–C₃, C₇ and C₉–C₁₀ LSMCA. The relative abundance of these size groups varied amongst the feedstocks cracked due to variations in the abundance of triunsaturated (linolenic), diunsaturated (linoleic) and monounsaturated (oleic) acids, respectively, in the original TG. We proposed a mechanism explaining the observed product speciation and homology profiles by the formation of acyloxyl biradicals as essential intermediates. High‐temperature C=C π‐bond hydrogenation with a concomitant σ‐bond cleavage yields C₉–C₁₀ LSMCA. This new path was confirmed by pyrolysis experiments with triolein in a GC pyroprobe.     

Production of Biodiesel Using Liquid Lipase Formulations

Looking back at the literature for enzymatic biodiesel, it is evident that the research has been focused on using immobilized lipase to enable re‐use of the enzyme due to price constraints on lipases used for catalyzing the transesterification process. The use of liquid formulations of lipase for biodiesel has recently been implemented in the industry. Technology for using liquid formulated lipases for enzymatic biodiesel production is new and, since enzyme prices have been reduced, it is now possible to simplify the process considerably and apply it for very low‐quality oils. In this paper, the use of liquid lipase formulations for enzymatic biodiesel will be described along with a general proposal for an industrial‐scale enzymatic biodiesel process with >95 % yield.     

Feruloylated Products from Coconut Oil and Shea Butter

The synthesis of feruloylated coconut oil and feruloylated shea butter were demonstrated in 0.5-L scale, shaken, batch reactions. Ethyl ferulate and the vegetable oil/fat were combined in a 1.0:1.3 mol ratio in the presence of Candida antartica lipase B immobilized on an acrylic resin (Novozym 435) at 60 °C. The transesterification of ethyl ferulate with coconut oil and shea butter reached equilibrium conversions, after 22 days, of 63 and 70%, respectively, with the shea butter transesterifications producing a white precipitate not observed in the coconut oil transesterifications. The faster transesterification rates, equilibrium conversions and white precipitate were shown to result from di- and monoacylglycerols (DAG and MAG) present in the shea butter. The transesterification of ethyl ferulate and coconut oil was also tested in a continuous, enzymatic, packed-bed bioreactor using Novozym 435 at 60 °C to produce feruloylated coconut oil at rates of 0.5–0.9 kg/day over 4.5 months. The feruloylated coconut oil acylglycerol species were identified by LC–MS analysis of transesterification reactions of ethyl ferulate with medium chain triacylglycerol (TAG) standards, C8–C14. The feruloylated vegetable oils possessed an ultra violet (UV) absorbing λ _max 328 nm, making them good UVAII absorbers, as defined by the U.S. Food and Drug Administration. The feruloylated coconut oil possessed a 17.5% higher absorption capacity than feruloylated shea butter on a per weight basis. All the feruloylated vegetable oils possessed rapid antioxidant capacity (50% reduction of initial radical concentration <5 min) at the concentrations tested, 0.5–2.5 mM. Feruloylated coconut oil possessed chemical and physical characteristics that suggested it would be fungible for feruloylated soybean oil in current retail formulations.     

Soybean Oil-Based Polyurethane Networks: Shape-Memory Effects and Surface Morphologies

Vegetable oil‐based shape‐memory polyurethane networks are an emerging class of bio‐based functional materials with great potential applications. In this study, a series of different structural soybean oil polyols were synthesized, and utilized to fabricate polyurethane networks by reacting with 1,6‐diisocyanatohexane. The soybean oil‐based polyurethanes (SOPUs) were characterized with differential scanning calorimetry (DSC), dynamic mechanical tests (DMA), tensile testing, shape‐memory testing, and atomic force microscopy (AFM). It was found that SOPUs with a preserved triglyceride structure were fixed in a temporary shape at ?20 °C, while others were fixed in temporary shapes at 4 °C. Although the recovery speeds were different, all the samples could completely regain their permanent shapes at 37 °C (human body temperature). Furthermore, different SOPUs exhibited different surface structures, which might provide the materials with additional values.     

Retardation of Crystallization of Diacylglycerol Oils Using Polyglycerol Fatty Acid Esters

Liquid oil containing high concentrations of diacylglycerols (DAG > 80 %, hereafter referred to as DAG-rich oil) is generally more likely to cause precipitation at chilled temperatures (clouding phenomena) than triacylglycerol-based oil. The clouding phenomena that occur during long-term storage of DAG-rich oil are unwanted in consumer products and therefore, must be prevented. In the present study, we attempted to retard precipitation by adding food emulsifiers, polyglycerol fatty acid esters (PGFE) containing different fatty acid moieties. DSC, polarized optical microscopy, and X-ray diffraction studies revealed that the addition of 0.2 % PGFE containing palmitic and oleic acid moieties very effectively retarded precipitation in the DAG-rich oil. To confirm these observations, we prepared a model DAG oil to mimic DAG-rich oil and examined the retardation behavior of high-melting DAG fractions using PGFE. The results are discussed in terms of the effects of PGFE additives on the pre-nucleation processes of high-melting fractions in DAG-rich oil.     

Optimization of the in Situ Transesterification of Grain Sorghum (Milo) DDGS to Fatty Acid Methyl Esters and Fatty Acid Ethyl Esters

Distillers grains and solubles generated from the ethanol fermentation of grains contain acylglycerols (AG) that can be successfully converted to fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAEE), commonly known as biodiesel. However, when grain sorghum (milo) DDGS were used as a feedstock for in situ transesterification (IST) under the previously established optimal conditions for other AG-bearing substrates, the yield plateaued at only 32.2% (corrected in this study to 24.2%). Several IST studies have reported significantly higher conversions of AG-bearing substrates to FAME. Therefore, the goal of this IST study was to improve the conversion of the AG in milo DDGS to FAME and FAEE by varying the temperature of reaction, the concentrations of the base (sodium methylate, NaOMe), volume of methanol and ethanol, and the amount of moisture in DDGS. Methyl tert-butyl ester was also evaluated as a co-solvent intended to improve miscibility and reaction rate. Among these variables, the most effective change was an increase in temperature from 40 to 65 °C. The most successful reaction used a AG:NaOMe:MeOH molar ratio of 1.0:2.6:168.9. Those reaction conditions used 4.8 mmol NaOMe dissolved in 12.6 mL MeOH and resulted in a 79.8% conversion of AG to FAME.     

原儿茶酸烷基酯在水包油乳液中的抗氧化行为

以原儿茶酸(PA)和系列正烷基醇为原料,采用直接酯化法合成了4种PA烷基酯。用IR和1HNMR表征了其结构,用DPPH法和ABTS法测定了其自由基清除能力,用Schaal烘箱实验考察了其在水包油乳液中的抗氧化效率。结果表明,PA酯化后增强了其对自由基的清除能力,并且随着烷基链长的增加清除能力增强。PA酯化提高了其在水包油乳液中的抗氧化效率,并随烷基链长的增加,抗氧化效率先增大后下降,原儿茶酸辛酯的抗氧化效率最佳。各种PA烷基酯在乳化剂吐温20的体积分数为4%、油与水体积比2∶8的菜籽油乳液中的抗氧化效率最佳。与添加PA的乳液相比,添加PA烷基酯的乳液的共轭二烯含量(CD)值达到1的时间以及p-茴香胺含量(AV)值达到6的时间均显著增加。     

The General Applicability of in Situ Transesterification for the Production of Fatty Acid Esters from a Variety of Feedstocks

We previously described a method for fatty acid methyl ester (FAME) production wherein acylglycerol transesterification was achieved by reacting flaked full fat soybeans with alkaline methanol to create a product that met ASTM specifications for biodiesel. In the present work we explore the general applicability of this approach, termed in situ transesterification, to feedstocks other than soybeans. Materials investigated were distillers dried grains with solubles (DDGS), which is a co-product of the production of ethanol from corn, and meat and bone meal (MBM), a product of animal rendering. For both feedstocks, reaction conditions giving maximum lipid transesterification were predicted by statistical experimental design and response surface regression analysis, and then verified experimentally. Successful transesterification was achieved at ambient pressure and 35 °C. For DDGS, partial drying markedly reduced the methanol requirement to achieve a high degree (91.1% of maximum theoretical) of transesterification. Elevated reaction temperatures (to 55 °C was explored) caused little or no shortening of the time to completion. Protein was not removed from the DDGS during this treatment. For MBM, drying was not required to achieve a high degree (93.3%) of transesterification. The remaining meal retained approximately 90% of the protein originally present. Coupled with the previous work with soybeans, the data presented here indicate that in situ transesterification is generally applicable to lipid-bearing materials, which could substantially increase the supply of biodiesel. Mention of brand or firm names does not constitute an endorsement by the US Department of Agriculture over others of a similar nature not mentioned.     

Production of Fatty‐Acid Methyl Esters Via the In Situ Transesterification of Grain Sorghum Bran and Sorghum Distiller's Dried Grains and Solubles

The acylglycerols (AG) in sorghum bran and distiller's dried grains and solubles (DDGS) from sorghum postfermentation have been converted to fatty‐acid methyl esters (FAME) using an in situ transesterification method. The reactions were conducted at 25 or 40 °C by incubating 8 g of feedstock, containing 1.3–2.4 mmol AG, in a solution of 2.4 or 4.8 mmol of NaOMe dissolved in 6.4 or 12.8 mL MeOH. The experimental results confirmed that reducing the moisture to approximately 2% (w/w) within the feedstock was necessary for the reaction to proceed. All of the reactions were monitored using high‐performance liquid chromatography and all performed better at 40 °C than at 25 °C. The most successful reactions used a AG:NaOMe:MeOH molar ratio of 1.0:2.0:131.7. Those reactions used 4.8 mmol NaOMe dissolved in 12.8 mL MeOH producing up to 98.3% FAME when sorghum bran was used as the feedstock. When DDGS from sorghum were used as the feedstock, the yield averaged 32.2% under the previously established optimal conditions.     

Formation and Microstructures of Whipped Oils Composed of Vegetable Oils and High-Melting Fat Crystals

This paper reports the experimental results of processes used for the formation of whipped oils composed of vegetable oils (salad oil) and high‐melting fat crystals [fully hydrogenated rapeseed oil rich in behenic acid (FHR‐B)]. No emulsifier was added to form this whipped oil. Microprobe FT‐IR spectroscopy, synchrotron radiation microbeam X‐ray diffraction (SR‐μ‐XRD), polarized optical microscopy, and differential scanning calorimetry (DSC) were employed to observe fine fat crystal particles of the most stable polymorph of β (β‐fat crystal), FHR‐B, and their adsorption at the air–oil surface before, during, and after the formation of the whipped oil. The results obtained revealed the following: (1) The preparation of an organogel composed of salad oil and small fibrous β‐fat crystals using a special tempering procedure was a prerequisite for forming whipped oil. (2) The β‐fat crystals were adsorbed at the air–oil surface to encapsulate the air bubbles during the formation process of whipped oil. (3) The values of overrun of the whipped oil reached >200 % after an aeration time of 30 min at 20 °C. (4) The SR‐μ‐XRD experiments demonstrated that the lamellar planes of the β‐fat crystals near the air–oil surface were arranged almost parallel to the air–oil surface plane. The present study provides the first evidence that tiny fat crystal particles may cause aeration in liquid oils without the addition of other whip‐assisting substances such as emulsifier crystals.     

Influence of Sophorolipid Structure on Interfacial Properties of Aqueous-Arabian Light Crude and Related Constituent Emulsions

Sophorolipids (SLs) offer an “environmentally friendly” alternative to chemically produced surfactants currently used in formulations for crude oil extraction, processing, and reclamation. Studies herein describe how sophorolipid structure influences its interfacial properties for environmentally and industrially relevant oil–water systems where the oil phase is Arabian light crude oil, paraffin oil, decane, hexadecane, a 1:1 vol/vol mixture of o-xylene and 1,2-dimethylcyclohexane, or a mixture of paraffin oil, o-xylene, and 1,2-dimethylcyclohexane (synthetic crude oil). SL-hexyl ester (SL-HE) reduces the crude oil–water interfacial tension (IFT) by 57 and 91% at 0.001 and 0.5 mg/mL, respectively. Crude oil displacement tests reveal that SL-ethyl ester (SL-EE) and SL-HE contract a crude oil slick on water to about 20% of its starting volume allowing for easier burning of spilled crude oil on marine surfaces. Water retention and emulsion phase (e.g., o/w vs. w/o) are determined by SL-structure/concentration, oil concentration, and oil composition to understand their performance for crude oil transportation and clean-up. For the first time, w/o emulsions were obtained using SLs and their formation occurred after homogenization when the oil phase consisted of a 1:1 mixture of o-xylene and 1,2-dimethylcyclohexane. Generally, the performance of SL-esters in the above studies was superior to that using Triton X-100, a comparison nonionic surfactant. Hence, SL-esters offer a valuable platform for tuning interfacial properties to optimize surfactant performance.     

Production and Emulsifying Effect of Polyglycerol and Fatty Acid Esters with Varying Degrees of Esterification

Esters with acyl groups can be formed by the esterification of polyglycerol. The purpose of the present study was to produce fatty acid esters [hexanoic (caproic), octanoic (caprylic), decanoic (capric), dodecanoic (lauric), tetradecanoic (myristic), hexadecanoic (palmitic), octadecanoic (stearic)] and polyglycerol (average number‐of degrees of polymerization of 5) with varying degrees of esterification and to examine their emulsifying properties. A number of fundamental catalysts of polyglycerol acylation reactions by methyl esters of carboxylic acid were studied, and sodium methoxide was found to be the best choice. The temperature rate of transesterification increased from 180 to 220 °C with the fatty acid chain alkyl residue. Synthesized mono‐, di‐, tri‐, tetra‐, and heptaesters of various fatty acids and polyglycerol provided the highest hydroxyl values from 15 to 815 mg KOH g^?1 and saponification values from 82 to 321 mg KOH g^?1. The emulsifying properties were assessed for all polyglycerol and fatty acid esters, with results showing maximum emulsifying effect for tri‐ and tetraesters of capric, lauric, and caprylic acids. Regardless of the hydrophilic–lipophilic balance value (HLB) of polyglycerol esters and carboxylic acid, a 4:1 ratio of sunflower oil to water formed a water‐in‐oil type emulsion. When mixing oil and water in a 1:1 ratio, mono‐ and diesters of polyglycerol formed an oil‐in‐water type emulsion, heptaesters formed a water‐in‐oil type emulsion, and tri‐ and tetraesters formed both of types of emulsions, depending on the length of the acid hydrocarbon radicals.     

Isothermal Curing Kinetics of Epoxidized Fatty Acid Methyl Esters and Triacylglycerols

Plant oil triacylglycerols are attractive renewable resources for biobased epoxy resins. We investigated the curing kinetics of three model epoxidized fatty acid methyl esters and representative epoxidized triacylglycerols with varied epoxide functionalities and distributions in the presence of a latent cationic initiator. Isothermal differential scanning calorimetry (DSC) was used to analyze the curing kinetics of the epoxy systems, and kinetic parameters (i.e., rate constants, reaction orders) were determined. Both epoxidized fatty esters and triacylglycerols followed the autocatalytic curing mechanism, and the DSC data were analyzed according to the Kamal autocatalytic model. Epoxidized methyl linoleate (EMLO) had the highest maximum curing rate, followed by epoxidized methyl linolenate (EMLON), and epoxidized methyl oleate (EMO) had the lowest maximum curing rate. We conclude that EMLO with two epoxide groups has the highest reactivity in this curing system, while the EMO with one epoxide group has the lowest reactivity. For epoxidized triacylglycerols, epoxidized camelina oil had the highest curing reactivity at higher temperatures, followed by epoxidized linseed oil and soybean oil.     

Rapid FT-NIR Analysis of Edible Oils for Total SFA, MUFA, PUFA, and Trans FA with Comparison to GC

Declarations of the total content of trans fatty acids (FA) and saturated FA (SFA) are mandatory on food labels in the US and Canada. Gas chromatography (GC) has been the method of choice for the determination of FA composition. However, GC is time consuming and requires conversion of fats and oils to their FA methyl esters. In the present study, a recently published Fourier transform near-infrared (FT-NIR) spectroscopic procedure was applied to the rapid (<5 min) determination of total SFA, monounsaturated FA (MUFA), polyunsaturated FA (PUFA), and trans FA contents of 30 commercially available edible fats and oils. Good agreement was obtained between the GC and FT-NIR methods for the determination of total SFA, MUFA, and PUFA contents. Differences between the two methods were apparent for the determination of trans fat at trans fat levels <2 % of total fat. The analytical determinations of total SFA, MUFA, and PUFA contents for many of the oils examined differed from the respective values declared on the product labels. Our findings demonstrate that the FT-NIR procedure serves as a suitable alternative method for the rapid determination of total SFA, MUFA, PUFA and trans FA contents of neat vegetable oils.     

The Role of Peracetic Acid in Bloodmeal Decoloring

Hydrogen peroxide (HP) can degrade soluble heme, forming yellow or colorless degradation products. Thermal treatment during bloodmeal production changes the conformation of oxyhemoglobin trapping heme in hydrophobic protein regions or forms methemoglobin (metHb) heme which catalytically removes HP. As a result, HP can only degrade a portion of the heme present in bloodmeal leading to poor decoloring. Equilibrium peracetic acid (PAA) solutions can effectively decolor bloodmeal. This work assessed the ability of PAA to decolor bloodmeal and the mechanism by which it occurs. The inability of HP to decolor bloodmeal is determined by the fact that it is unable to permanently degrade metHb heme, or hydrophobically trapped heme. Addition of organic acids to HP led to significant swelling of the protein chains but also to poorer decoloring and lower HP consumption compared to PAA. This suggested that in the case of PAA solutions, where bleaching was facile, the reason PAA solutions are capable of decoloring bloodmeal was due to the action of the PAA molecule against heme, whereas HP and acetic (ethanoic) acid played only minor roles in total bleaching. The decolored protein powder has reduced odor and whiter color, and is suitable for applications such as bioplastics.     

The Effect of Natural and Synthetic Antioxidants on the Oxidative Stability of Biodiesel

A significant problem associated with the commercial acceptance of biodiesel is poor oxidative stability. This study investigates the effectiveness of various natural and synthetic antioxidants [α-tocopherol (α-T), butylated hydroxyanisole (BHA), butyl-4-methylphenol (BHT), tert-butylhydroquinone (TBHQ), 2, 5-di-tert-butyl-hydroquinone (DTBHQ), ionol BF200 (IB), propylgallate (PG), and pyrogallol (PY)] to improve the oxidative stability of soybean oil (SBO-), cottonseed oil (CSO-), poultry fat (PF-), and yellow grease (YG-) based biodiesel at the varying concentrations between 250 and 1,000 ppm. Results indicate that different types of biodiesel have different natural levels of oxidative stability, indicating that natural antioxidants play a significant role in determining oxidative stability. Moreover, PG, PY, TBHQ, BHA, BHT, DTBHQ, and IB can enhance the oxidative stability for these different types of biodiesel. Antioxidant activity increased with increasing concentration. The induction period of SBO-, CSO-, YG-, and distilled SBO-based biodiesel could be improved significantly with PY, PG and TBHQ, while PY, BHA, and BHT show the best results for PF-based biodiesel. This indicates that the effect of each antioxidant on biodiesel differs depending on different feedstock. Moreover, the effect of antioxidants on B20 and B100 was similar; suggesting that improving the oxidative stability of biodiesel can effectively increase that of biodiesel blends. The oxidative stability of untreated SBO-based biodiesel decreased with the increasing indoor and outdoor storage time, while the induction period values with adding TBHQ to SBO-based biodiesel remained constant for up to 9 months.     

聚丙烯酸酯乳液生产工艺研究

聚丙烯酸酯外用乳胶漆其优良的性能主要决定于丙稀酸脂聚合乳液的性能。从聚丙稀酸脂单体、聚丙烯酸酯的乳化聚合、配方及助剂等方面对生产操作及工艺研究进行了探讨,以获得质量更佳的乳液,确保漆膜的优良特性。     

Investigation of Oil and Protein Contents of Eight Sudanese Lagenaria siceraria Varieties

The composition of the oil and protein contents of eight Lagenaria siceraria varieties was characterized in order to evaluate their suitability as a source of edible oil and protein. The physicochemical properties and fatty acids of seed oils were determined. The oil yield ranged from 24.11 to 26.32 %. The refractive indices and relative densities of the oils fell within the narrow ranges of 1.464–1.468 and 0.857–0.907 g/cm³, respectively. The saponification value ranged from 158.48 to 179.52 mg KOH/g, unsaponifiable matter was between 0.749 and 0.937 %, and the peroxide values were lower than Codex values for vegetable oils. The principal fatty acids were linoleic (62.1–67.9 %), oleic (11.54–15.46 %), palmitic (12.13–14.03 %), and stearic (6.71–7.71 %) acids. Low linolenic acid levels were also observed (<1 %) within the range of 0.32–0.44 %. The major essential amino acids were arginine (2.04–3.77 g/100 g), leucine (1.245–1.726 g/100 g), phenylalanine (0.803–1.396 g/100 g), and lysine (0.921–1.383 g/100 g). The non‐essential amino acids were glutamic acid (2.5–4.37 g/100 g), aspartic acid (1.39–2.36 g/100 g), serine (0.69–1.19 g/100 g), glycine (0.79–1.37 g/100 g), alanine (0.72–1.37 g/100 g), and proline (0.63–1.02 g/100 g). Nine minerals (Na, Ca, Mg, K, Cu, Fe, Mn, Zn, and P) were determined with significant (p < 0.05) differences. The studied oils showed promising results and can be used in the food, cosmetics, and pharmaceutical industries. This is the first study on the eight L. siceraria seed varieties grown in Sudan, opening the way for further studies on these seeds.     

油脂水解生产脂肪酸工艺选择

文章阐述了以天然油脂为原料生产脂肪酸的发展前景,分析了影响油脂水解的因素,详细介绍了工业上常用的三种油脂水解的生产工艺,并对最先进的生产工艺做出选择。     

Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid

This work describes two sustainable methods for production and purification of azelaic acid (AA) to replace the current process of ozonolysis of oleic acid (OA). The first proceeds in two steps, coupling smooth oxidation of OA to 9,10‐dihydroxystearic acid (DSA) with subsequent oxidative cleavage by sodium hypochlorite. An alternative methodology is also proposed, using a chemocatalytic system consisting of H₂O₂/H₂WO₄ for direct oxidative cleavage of the double bond of OA at 373 K. A convenient technique for separation and purification of azelaic acid is also proposed.