Phase-transfer catalysis and ultrasonic waves II: saponification of vegetable oil.

Saponification of oils which is a commercially important heterogeneous reaction, can be speeded up by the application of ultrasound in the presence of phase-transfer catalyst (PTC). This paper focuses on the ability of ultrasound to cause efficient mixing of this liquid-liquid heterogeneous reaction. Castor oil was taken as a model oil and the kinetic of the reaction was followed by the extent of saponification. The hydrolysis of castor oil was carried out with different PTC such as cetyl trimethyl ammonium bromide (CTAB), benzyl triethyl ammonium chloride (BTAC) and tetrabutyl ammonium bromide (TBAB) in aqueous alkaline solution. As hydroxyl anion moves very slowly from aqueous to oil phase, the presence of a PTC is of prime importance. For this purpose, cationic surfactants are selected. The sonication of biphasic system were performed by 20 kHz (simple horn and cup horn) and 900 kHz. It was found that CTAB was better than the two others and this could be related to the molecular structure of the PTCs. The effect of temperature was also studied on the saponification process. By increasing the temperature, the yield was also increased and this could be explained by intermolecular forces, interfacial tension and mass transfer. Saponification of three different vegetable oils shows that the almond oil is saponified easier than the two others and this could be related to their properties such as surface tension, viscosity and density.     

Sonocrystallization: effect on lactose recovery and crystal habit

Sonocrystallization is the use of power ultrasound to control the crystallization process, commonly used during the nucleation phase of crystallization. However, in the present study a different approach has been tried, in which the whole process of lactose crystallization from model reconstituted lactose solutions was completed rapidly with the aid of ultrasound, in the presence of 'ethanol' as an anti-solvent, at temperature of 30+/-2 degrees C (ambient temperature). The lactose recovery and crystal properties from sonicated samples were compared with non-sonicated samples. For optimization of sonocrystallization process for rapid lactose recovery, variations in the time of sonication, lactose concentration, protein concentration and pH were tried. A lactose recovery of 91.48% was obtained in 5 min of sonication time, from a reconstituted lactose solution (17.5% w/v, pH 4.2) as against 14.63% under only stirring. Lactose recovery decreased with lowering of pH from 4.2 to 2.8. The protein showed maximum influence on lactose recovery even at concentration of 0.2% w/v. A rapid process of crystallization gave a better uniformity in crystal size distribution of lactose samples.     

Sono-synthesis of imidazolidine-2-thione as a base compound of some pharmaceutical products

This work describes the results of investigations carried out to investigate the synthesis of imidazolidine-2-thione as a heterocyclic compound in the presence of ultrasound (sono-synthesis) and in the absence of ultrasound (conventional method). Instead of reflux in the conventional method, the mixture was sonicated indirectly in sono-synthetic method with 500 kHz at different temperatures. Some experiments were also carried out without catalyst with 500 and 900 kHz. In the conventional method, the yield of the reaction was increased by increasing the temperature but in sono-synthetic method, the thermal dependence was different in the range of temperature studied (10-50 degrees C). In the presence of ultrasound, the yield was reached to more than 93% after 1h but in the conventional method it reached only 27% under the same conditions. Comparison was carried out with and without catalyst. It is also possible to achieve a high yield of product under sonication without the use of a catalyst.     

基于植物油可见吸收光谱的相关系数鉴别特级初榨橄榄油

目前市场上的橄榄油品牌很多,质量参差不齐,亟需完善橄榄油的等级分类检测和特级初榨橄榄油的鉴别方法。可见吸收光谱光谱法可在不直接接触样品的情况下对样品进行无添加试剂的探测,因此为实现特级初榨橄榄油的鉴别,采用可见吸收光谱法对不同种类植物油进行了光谱测量。实验结果发现特级初榨橄榄油在500~780 nm波段内具有4个明显的吸收峰,而其他种类植物油在此波段内吸光度较弱或无吸收峰,且同种植物油不同品牌之间的光谱特征极其相似。采用相关系数比对不同种类植物油可见吸收光谱,分别计算了四个不同波长范围内植物油的可见吸收光谱的相关系数,实验发现不同波长范围内的植物油可见光谱相关系数差别较大。在520～700 nm范围内,特级初榨橄榄油间的光谱相关系数在0.999 6以上,特级初榨橄榄油与其他种类植物油的光谱相关系数均低于0.267 8,特级初榨橄榄油与其他等级橄榄油的光谱相关系数在0.194 6～0.835 8之间。研究结果表明可见吸收光谱相关系数法是一种快速非接触式鉴别特级初榨橄榄油的可行性方法。建立了一种特级初榨橄榄油快速鉴别方法,即可见吸收光谱相关系数法。该方法在特级初榨橄榄油的实际鉴别中具有一定的应用价值。     

Influence of bleaching by ultrasound on fatty acids and minor compounds of olive oil. Qualitative and quantitative analysis of volatile compounds (by SPME coupled to GC/MS)

The effects of bleaching using high power ultrasound (20 kHz) on the quality of olive oil were considered in this study, in order to verify the modifications that can occur in fatty acid composition and minor compounds. During the treatment of olive oil under ultrasonic waves, a rancid odour has been detected. Treated olive oils show no significant changes in their chemical composition but the presence of some volatile compounds, due to ultrasonic treatment. Some off-flavour compounds (hexanal, hept-2-enal and 2(E),4(E)-decadienal) resulting from the sonodegradation of olive oil have been identified. A wide variety of analytical techniques (GLC, HPLC and GC/MS) were used to follow the quality of bleached olive oils with ultrasonic waves by the determination of the amounts of certain minor compounds such as sterols and tocopherols. Steradienes, resulting from the dehydration of sterols, were detected with small quantities especially in severe conditions of sonication. Solid phase micro-extraction (SPME) coupled to gas chromatography was known to be a sensitive technique to follow changes in the oxidative state of vegetable oils by measuring the amount of volatile materials produced during the refining process.     

Fatty acids methyl esters from vegetable oil by means of ultrasonic energy

The transesterification of vegetable oil with short-chain alcohols, in the presence of base-catalyst, by means of low frequency ultrasound (28 and 40 kHz) in order to obtain biodiesel fuel was studied. By using ultrasounds the reaction time is much shorter (10-40 min) than for mechanical stirring. The quantity of required catalyst is 2 or 3 times lower. The molar ratio of alcohol/oil used is only 6:1. Normal chain alcohols react fast, while secondary and tertiary alcohols show some or no conversion after 60 min of reaction. Surprisingly, 40 kHz ultrasounds are much more effective in the reduction of the reaction time (10-20 min). Twenty eight kilohertz give slightly better yields (98-99%), but longer reaction time, while higher frequencies are not useful at all for the transesterification of fatty acids.     

Green ultrasound-assisted extraction of carotenoids from pomegranate wastes using vegetable oils

The objective of this work was to develop a new process for pomegranate peels application in food industries based on ultrasound-assisted extraction of carotenoids using different vegetable oils as solvents. In this way, an oil enriched with antioxidants is produced. Sunflower oil and soy oil were used as alternative solvents and the effects of various parameters on extraction yield were studied. Extraction temperature, solid/oil ratio, amplitude level, and extraction time were the factors investigated with respect to extraction yield. Comparative studies between ultrasound-assisted and conventional solvent extraction were carried out in terms of processing procedure and total carotenoids content. The efficient extraction period for achieving maximum yield of pomegranate peel carotenoids was about 30 min. The optimum operating conditions were found to be: extraction temperature, 51.5 °C; peels/solvent ratio, 0.10; amplitude level, 58.8%; solvent, sunflower oil. A second-order kinetic model was successfully developed for describing the mechanism of ultrasound extraction under different processing parameters.     

High-power ultrasound in olive paste pretreatment. Effect on process yield and virgin olive oil characteristics

The effect of high-power ultrasound on olive paste, on laboratory thermo-mixing operations for virgin olive oil extraction, has been studied. Direct sonication by an ultrasound probe horn (105 W cm⁻² and 24 kHz) and indirect sonication with an ultrasound-cleaning bath (150 W and 25 kHz) were applied and their effects compared with the conventional thermal treatment.

A quick-heating of olive paste, from ambient (12–20 °C) to optimal temperature conditions (28–30 °C), and an oil extractability improvement were observed when applying sonication. Better extractability was obtained by direct sonication for high moisture olives (>50%) whereas indirect sonication gave greater extractability for low moisture olive fruits (<50%).

Optimal application of ultrasound was achieved with direct sonication for 4 min at the beginning of paste malaxation and with indirect sonication during the malaxation time.

Effect of high-power ultrasound on oil quality parameters and nutritional and sensory characteristics were studied. Changes in quality parameters (free acidity value, peroxide value, K270 and K232) were not found, however significant effects on the levels of bitterness, polyphenols, tocopherols (vitamin E), chlorophyll and carotenoids were observed. Oils from sonicated pastes showed lower bitterness and higher content of tocopherols, chlorophylls and carotenoids. Related to sensory characteristics, off-flavour volatiles were not detected in oils from sonication treatments. Total peak areas of volatiles and the ratio hexanal/E-2-hexenal, as determined by SPME analysis, were lower than non-sonicated reference oils; sensory evaluation by panel test showed higher intensity of positive attributes and lesser of negative characteristics than those untreated.     

Ultrasound for low temperature dyeing of wool with acid dye

The possibility of reducing the temperature of conventional wool dyeing with an acid levelling dye using ultrasound was studied in order to reach exhaustion values comparable to those obtained with the standard procedure at 98 °C, obtaining dyed samples of good quality. The aim was to develop a laboratory method that could be transferred at industrial level, reducing both the energy consumption and fiber damage caused by the prolonged exposure to high temperature without the use of polluting auxiliary agents.Dyeings of wool fabrics were carried out in the temperature range between 60 °C and 80 °C using either mechanical or ultrasound agitation of the bath and coupling the two methods to compare the results. For each dyeing, the exhaustion curves of the dye bath were determined and the better results of dyeing kinetics were obtained with ultrasound coupled with mechanical stirring. Hence the corresponding half dyeing times, absorption rate constants according to Cegarra-Puente modified equation and ultrasonic efficiency were calculated in comparison with mechanical stirring alone. In the presence of ultrasound the absorption rate constants increased by at least 50%, at each temperature, confirming the synergic effect of sonication on the dyeing kinetics. Moreover the apparent activation energies were also evaluated and the positive effect of ultrasound was ascribed to the pre-exponential factor of the Arrhenius equation. It was also shown that the effect of ultrasound at 60 °C was just on the dye bath, practically unaffecting the wool fiber surface, as confirmed by the results of SEM analysis.Finally, fastness tests to rubbing and domestic laundering yielded good values for samples dyed in ultrasound assisted process even at the lower temperature. These results suggest the possibility, thanks to the use of ultrasound, to obtain a well equalized dyeing on wool working yet at 60 °C, a temperature process strongly lower than 98 °C, currently used in industry, which damages the mechanical properties of the fibers.     

Impact of ultrasonic treatment process on pour point of vegetable oils based liquid insulation

This study presents an application of ultrasonic technology in the high voltage liquid insulation domain towards the reduction of pour point of vegetable oil samples for the utilization of vegetable oils as liquid insulation in cold climate areas on power transformers. Pour point reduction has been achieved by processing the vegetable oil samples by using ultrasonic treatment process with 100 W and 30 kHz ultrasonic waves for various exposure times of 15, 30, 45 and 60 min. Edible vegetable oils such as sunflower oil, palm oil, sesame oil and non edible vegetable oils such as honge oil, neem oil and punna oil are considered as two categories of vegetable oils for this experimental investigation. Ultrasonic treatment process results in the reduction of pour point of vegetable oils to meet out the standard value of pour point for liquid insulation as per IEEE Standard C57.147, 2018. A significant reduction in pour point temperature of vegetable oil samples have been obtained with an increased exposure time. The obtained variations in pour point after exposure with ultrasonic waves may be due to the possible changes in crystallization kinetics of fatty acids components of vegetable oil samples due to energy input of ultrasonic waves. The experimental results have given a way towards the positive encouragement and development with ultrasonic treatment for achieving low pour point vegetable oils as liquid insulation in power transformers for applications on cold climatic areas.     

Production of tung oil epoxy resin using low frequency high power ultrasound

Epoxy resins made from vegetable oils are an alternative to synthesize epoxy resins from renewable sources. Tung oil is rich in α -eleostearic fatty acid, which contains three double bonds producing epoxy resins with up to three epoxy groups per fatty acid. This work studied the production of tung oil epoxy resin using hydrogen peroxide as an oxidizing agent and acetic and formic acid as percarboxylic acid precursors, applying low frequency high power ultrasound. This study evaluated the effects of ultrasound power density, hydrogen peroxide concentration, acetic acid concentration, and formic acid concentration on the yield into epoxy resin, selectivity, and by-products formation. Application of ultrasound was carried out using a 19 kHz probe ultrasound (horn ultrasound) with a 1.3 cm diameter titanium probe, 500 W nominal power, 2940 W L⁻¹ maximum effective power density applied to the reaction mixture. Ultrasound technology yielded up to 85% of epoxy resin in 3 h of reaction. The use of formic acid resulted in a slightly lower oil conversion than acetic acid but with a much higher selectivity towards epoxidized tung oil. However, using acetic acid resulted in the production of high-value by-products, such as 2-heptenal and 2,4-nonadienal. The ultrasound-assisted epoxidation showed to be particularly efficient when applied to oils containing conjugated double-bonds.     

Palm oil hydrolysis catalyzed by lipases under ultrasound irradiation--the use of experimental design as a tool for variables evaluation

Diacylglycerol oil has been increasingly recognized by its good nutritional properties and therefore, different technologies have been developed for obtaining it. The present work focuses on the diacylglycerol production by hydrolysis reaction of the palm oil using the PS IM and TL IM commercial lipases as biocatalysts under ultrasound irradiation. An experimental design (central composite rotatable design - CCRD) adopting surface response was applied as a tool to evaluate the optimal reaction conditions beyond a restrict number of experiments. Reactions were performed in an ultrasound equipment and different variables were investigated, such as temperature (30-55 °C), enzyme content (1-2 wt.% of oil mass), mechanical stirring (300-700 rpm) and reaction time. Both, PS IM and TL IM enzymes showed the best results after 1 h and 30 min of reaction under 30 °C and, applying 300 rpm as stirring. On these conditions, the diacylglycerol yield was around 34% and 39%, respectively; considering that 1% PS IM was applied for the first one and, 2% TL IM for the second one. Therefore, it was obtained good yield of a diacylglycerol-rich oil in shorter reaction times under sonication and soft conditions. The mathematic model proposed suggested a satisfactorily representation of the process and good correlation among the experimental results and the theoretical values predicted by the model equation were achieved.     

Ultrasound pasteurization: the effects of temperature, soluble solids, organic acids and pH on the inactivation of Escherichia coli ATCC 25922

The objectives of this research were to study the effects of temperature, sugar concentration (8, 12, and 16 g/100ml), organic acids (citric and malic acids) and pH (2.5 and 4.0) on ultrasound pasteurization. The model organism used for the research was Escherichia coli ATCC 25922, and ultrasound treatment times were conducted to achieve a 5 log (base 10) reduction. Ultrasound generates heat, therefore the study involved removing the heat using a jacketed beaker with refrigerant (-30 degrees C) to maintain processing temperature at or below 30 degrees C and eliminate the thermal inactivation effects. Overall, ultrasound increased the sensitivity of E. coli to thermal inactivation. The presence of soluble solids had a protective effect where the sonication time requirement increased. Similar to heat sensitivity, the lower pH environment resulted in E. coli having less resistance to sonication. The type of organic acid had the least significant effect on ultrasound inactivation of E. coli.     

Sonochemical bromination of acetophenones using p-toluenesulfonic acid-N-bromosuccinimide.

Substituted acetophenones react with N-bromosuccinimide (NBS) and p-toluenesulfonic acid (p-TsOH) in the presence of ultrasound in methanol at 35 +/- 2 degrees C to give alpha-bromoacetophenones in high yield. In the absence of ultrasound the reaction takes place at the boiling point of methanol (65 degrees C) and takes longer time. The reaction does not take place in the absence of p-TsOH thermally or sonically. However the reaction is possible under photochemical conditions in the absence of p-TsOH. The best solvent for the reaction was found to be methanol.     

荧光光谱法快速鉴别花生油、芝麻油和调和油

比较分析了不同品种、同品种不同厂家、不同批次的市售花生油、芝麻油、调和油的分子荧光光谱差异特征,结合系统聚类分析法进行品种鉴别。结果表明:3种食用植物油的荧光光谱图具有各自不同特征,同一品种不同厂家的谱图存在一定的差异,同品种同厂家不同批次的也有微小差异。提取荧光谱图特征信息,利用系统聚类和三维聚类识别模式,从宏观上简便、直观、快速地鉴别3种食用植物油的品种。     

Ultrasound-assisted dyeing of cellulose acetate

The possibility of reducing the use of auxiliaries in conventional cellulose acetate dyeing with Disperse Red 50 using ultrasound technique was studied as an alternative to the standard procedure. Dyeing of cellulose acetate yarn was carried out by using either mechanical agitation alone, with and without auxiliaries, or coupling mechanical and ultrasound agitation in the bath where the temperature range was maintained between 60 and 80 °C.The best results of dyeing kinetics were obtained with ultrasound coupled with mechanical agitation without auxiliaries (90% of bath exhaustion value at 80 °C). Hence the corresponding half dyeing times, absorption rate constants according to Cegarra–Puente modified equation and ultrasound efficiency were calculated confirming the synergic effect of sonication on the dyeing kinetics. Moreover the apparent activation energies were also evaluated and the positive effect of ultrasound added to mechanical agitation was evidenced by the lower value (48 kJ/mol) in comparison with 112 and 169 kJ/mol for mechanical stirring alone with auxiliaries and without, respectively.Finally, the fastness tests gave good values for samples dyed with ultrasound technique even without auxiliaries. Moreover color measurements on dyed yarns showed that the color yield obtained by ultrasound-assisted dyeing at 80 °C of cellulose acetate without using additional chemicals into the dye bath reached the same value yielded by mechanical agitation, but with remarkably shorter time.     

Liquid-phase adsorption and desorption of phenol onto activated carbons with ultrasound

The effect of 48-kHz ultrasound on the adsorption and desorption of phenol from aqueous solutions onto coconut shell-based granular activated carbons was studied at 25 degrees C. Experiments were performed at different carbon particle sizes (1.15, 2.5, 4.0 mm), initial phenol concentrations (1.06-10.6 mol/m3), and ultrasonic powers (46-133 W). Regardless of the absence and presence of ultrasound, the adsorption isotherms were well obeyed by the Langmuir equation. When ultrasound was applied in the whole adsorption process, the adsorption capacity decreased but the Langmuir constant increased with increasing ultrasonic power. According to the analysis of kinetic data by the Elovich equation, it was shown that the initial rate of adsorption was enhanced after sonication and the number of sites available for adsorption was reduced. The effect of ultrasonic intensity on the initial rate and final amount of desorption of phenol from the loaded carbons using 0.1 mol/dm3 of NaOH were also evaluated and compared.     

Synthesis of glycoluril catalyzed by potassium hydroxide under ultrasound irradiation

Synthesis of the glycolurils catalyzed by potassium hydroxide was carried out in 17–75% yield at 40 °C in EtOH under ultrasound irradiation. Compared to the method using stirring, the main advantage of the present procedure is milder conditions and shorter reaction time.     

Investigations in physical mechanism of ultrasound-assisted antisolvent batch crystallization of lactose monohydrate from aqueous solutions

Sonication is known to enhance crystallization of lactose from aqueous solutions. This study has attempted to reveal the mechanistic features of antisolvent crystallization of lactose monohydrate from aqueous solutions. Experiments were conducted in three protocols, viz. mechanical stirring, mechanical stirring with sonication and sonication at elevated static pressure. Mechanical stirring provided macroconvection while sonication induced microconvection in the system. Other experimental parameters were initial lactose concentration and rate of antisolvent (ethanol) addition. Kinetic parameters of crystallization were coupled with simulations of bubble dynamics. The growth rate of crystals, rate of nucleation, average size of crystal crop and total lactose yield in different protocols were related to nature of convection in the medium. Macroconvection assisted nucleation but could not give high growth rate. Microconvection comprised of microstreaming due to ultrasound and acoustic (or shock) waves due to transient cavitation. Sonication at atmospheric static pressure enhanced growth rate but reduced nucleation. However, with elimination of cavitation at elevated static pressure, sonication enhanced both nucleation and growth rate resulting in almost complete lactose recovery.     

Growth rate of potash alum crystals: comparison of silent and ultrasonic conditions

The influence of power ultrasound on the growth rate of potash alum was investigated. The experiments on growth of potash alum crystals were carried out in a stirred double jacket tank in silent conditions as well as in the presence of power ultrasound (20 kHz) at 32 degrees C, with different initial crystal sizes. It was observed that the mass growth rate of potash alum was faster under ultrasound compared to that under silent conditions. The shape was not modified by ultrasound but the size of crystals, which are grown under ultrasound, are smaller and with higher density compared to those grown under silent conditions.