Ultrasonic Pretreatment Transesterification for Solid Basic-Catalyzed Synthesis of Fatty Acid Methyl Esters

Generally, ultrasound irradiation is required throughout the reaction for fatty acid methyl esters (FAME, namely, biodiesel) production, which is energy-consuming and difficult to scale-up. In order to improve the industrial application of ultrasonic technology, a systematic study of ultrasonic pretreatment solid basic (Na₂SiO₃)-catalyzed transesterification for FAME production from cottonseed oil was carried out, and the effect of ultrasonic waves on the properties of Na₂SiO₃ catalyst was assessed by X-ray diffraction (XRD), Fourier transform Infrared (FTIR) and scanning electron microscopy (SEM) characterization of fresh and collected catalysts. An ultrasonic frequency of 30 kHz, ultrasonic power of 200 W and ultrasonic pretreatment irradiation time of 30 min was determined to guarantee a satisfactory degree of transesterification. The optimum production was achieved in the reaction system at 45 °C with methanol/cottonseed oil molar ratio 5:1, catalyst dosage 3% and stirring speed 350 rpm resulting in a FAME yield of above 97% after 60 min of reaction under mechanical stirring with the ultrasonic pretreatment process. The new process has a shorter reaction time, a more moderate reaction temperature, a less amount of methanol and catalyst than only the mechanical stirring process without essential damage to activity and the structure of catalyst. These results are of great significance for applying the ultrasonic pretreatment method to produce FAME.     

Comparative Study of Tocopherol Contents and Fatty Acids Composition in Twenty Almond Cultivars of Afghanistan

Afghanistan is the fourth largest producer of almonds in the world producing 78 native and 6 imported cultivars. However, till date, there have been no comprehensive data on nutrient profiles of the native cultivars. Thus, in the present investigation, tocopherol contents and fatty acid composition from the kernels of 20 selected native almond cultivars of Afghanistan were analyzed. The ranges of variability for the studied nutrients were similar to those already reported for almonds grown in other countries, such as 47.8–66.1% of total lipids (fresh weight basis), 62.54–81.57% of oleic acid in the total lipids, and 139.1–355.0 μg/g α-tocopherol in kernels. With respect to cultivars, significantly (p < 0.05) high content of total lipids were recorded in ‘Belabai’ and ‘Sattarbai’ (Afghan grade), oleic acid in ‘Khairodini’ and of α-tocopherol in ‘Khairodini-161 Samangan’ and ‘Belabai’ cultivars. Kernels from these cultivars can be used for nutrient dense food formulations. Daily consumption of 50 g almonds is sufficient to meet the RDA of α-tocopherol (15 mg/day), considering the average 300 μg/g of α-tocopherol in Afghan almonds. Also, these nutrient rich cultivars can be used in almond breeding programs globally, to focus on improving kernel oil composition and nutrient contents.     

Relationships between base-catalyzed hydrolysis rates or glutathione reactivity for acrylates and methacrylates and their NMR spectra or heat of formation

The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs) between the base-catalyzed hydrolysis rate constants (k1) or the rate constant with glutathione (GSH) (log k(GSH)) for acrylates and methacrylates and the (13)C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δC(α) and δC(β)) or heat of formation (Hf) calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δC(β), but not δC(α), was obtained for methacrylates (r(2) = 0.93), but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r(2) = 0.89). By contrast, log k(GSH) for acrylates and methacrylates was linearly related to their δC(β) (r(2) = 0.99), but not to Hf. These findings indicate that the (13)C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.     

High Yield of Wax Ester Synthesized from Cetyl Alcohol and Octanoic Acid by Lipozyme RMIM and Novozym 435

Wax esters are long-chain esters that have been widely applied in premium lubricants, parting agents, antifoaming agents and cosmetics. In this study, the biocatalytic preparation of a specific wax ester, cetyl octanoate, is performed in n-hexane using two commercial immobilized lipases, i.e., Lipozyme^® RMIM (Rhizomucor miehei) and Novozym^® 435 (Candida antarctica). Response surface methodology (RSM) and 5-level-4-factor central composite rotatable design (CCRD) are employed to evaluate the effects of reaction time (1–5 h), reaction temperature (45–65 °C), substrate molar ratio (1–3:1), and enzyme amount (10%–50%) on the yield of cetyl octanoate. Using RSM to optimize the reaction, the maximum yields reached 94% and 98% using Lipozyme^® RMIM and Novozym^® 435, respectively. The optimum conditions for synthesis of cetyl octanoate by both lipases are established and compared. Novozym^® 435 proves to be a more efficient biocatalyst than Lipozyme^® RMIM.     

Effects of High Temperatures and Duration of Heating on Olive Oil Properties for Food Use and Biodiesel Production

Heating deteriorates the physicochemical properties of a vegetable oil for both edible and biofuel uses. The parameters for edible olive oil are established by European Union regulations and by the International Olive Council. The properties of a vegetable oil to be used as a source for biodiesel production are indicated by the German DIN 51605 for rapeseed oil. Biofuel properties are described by the European EN 14214 and the North American ASTM 6751 standards for biodiesel. It is useful to know how temperature and heating duration influence the physicochemical properties of olive oil. Free acidity, refractive index and myristic acid were not significantly influenced by temperature and heating duration. K232, K266, K270, K274, p-anisidine value, totox index, kinematic viscosity (at 30, 40, 50 °C), estimated higher heating value, relative density, and cetane number increased during olive oil heating. The biological properties: iodine value, oxidative stability index, antiradical (2,2-diphenyl-1-picrylhydrazyl radical, DPPH?) activity, and phenol content, decreased when time and temperature increased. Fatty acid methyl esters were highly influenced by the applied variables. Almost all the fatty acid methyl esters, except myristic, stearic, and arachidic acid esters, were influenced by the combined effect of temperature and time in a very highly significant level. These results show how temperature and duration of heating influence extra virgin olive oil degradation for both edible use and biodiesel production.     

Factors Impacting the Formation of 3-MCPD Esters and Glycidyl Esters During Deep Fat Frying of Chicken Breast Meat

The effect of the frying temperature, frying duration and the addition of NaCl on the formation of 3‐monochloropropane‐1,2‐diol (3‐MCPD) esters and glycidyl esters (GE) in palm olein after deep frying was examined in this study. The eight frying systems were deep‐fat frying (at 160 and 180 °C) of chicken breast meat (CBM) (with 0, 1, 3 and 5% sodium chloride, NaCl) for 100 min/day for five consecutive days. All oil samples collected after each day were analyzed for 3‐MCPD ester, GE, and free fatty acid (FFA) contents, specific extinctions at 232 and 268 nm (K₂₃₂ and K₂₆₈), p‐anisidine value (pA), and fatty acid composition. There was a significant (p < 0.05) decrease in the 3‐MCPD esters and a significant (p < 0.05) decrease in the GE with the increasing of the frying duration. There were significant (p < 0.05) increases in the 3‐MCPD esters formed when the concentration of NaCl increased from 0 to 5%. The addition of NaCl to the CBM during deep frying had no significant effect on the GE generation. The FFA contents, K₂₃₂ and K₂₆₈ and pA showed that all the frying oils were within the safety limit.     

固体催化剂催化高酸值鱼油的甲酯化研究

以高酸值鱼油为原料,利用Amberlyst15固体酸催化剂在温和条件下进行酯化反应降低酸值,再由氧化钙固体碱催化剂催化转酯化得到鱼油脂肪酸甲酯。采用正交设计优化反应条件,预酯化：催化剂用量15%,反应温度75℃,n（醇）/n（油）14,反应时间1.5 h,酸值降为3.35 mg/g,二次预酯化酸值降至1.24 mg/g;酯交换：催化剂用量为10%,反应温度65℃,n（醇）/n（油）为6,反应时间为3 h,鱼油甲酯收率为93.7%。     

Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Continuous production of palm methyl esters

A system for continuous transesterification of palm oil was developed using a continuous stirred-tank reactor (CSTR) and pumps for continuous delivery of oil and catalyst and for continuous removal of product. Potassium hydroxide was used as the catalyst, the methanol-to-oil molar ratio was 6∶1, and reaction temperature was 60°C. The yield of methyl esters increased from 58.8% of theoretical yield at a residence time of 40 min to 97.3% at a residence time of 60 min. However, higher residence times decreased the production rate. During long-term continuous operation, the CSTR displayed steady state conditions in terms of product profile and methyl ester concentration. This process has good potential in the manufacture of biodiesel.     

Silicone emulsions and surfactants

This review is intended to supply the practicing chemist with a working knowledge of the chemistry of silicone compounds. It has been divided into two parts, the first dealing with basic chemistry of silicones [O'Lenic, A.J., JSD 2, 229 (2000)] and the second with silicone-based surfactants, specifically dimethicone copolyols and their derivatives. This is the second part of the review. Although silicone compounds have been known for over 50 yr, the chemistry of these materials remains elusive to the average formulating chemist. This is indeed unfortunate, since the chemistry of the silicon atom and silicone compounds is every bit as wide in scope and rich in content as the chemistry of the carbon atom and the surfactant chemistry upon which it is based. This article will deal with the various methods of delivering silicone from aqueous systems. The two approaches are (i) to make emultions that contain silicone oil and a surfactant pair and the (ii) to make modify the molecule chemically to make the product more water-compatible. Both approaches find applications in a variety of industrial applications, with different challenges to the formulator.