Ultrasound-assisted biodiesel production from Camelina sativa oil.

The main drawbacks of biodiesel production are high reaction temperatures, stirring and time. These could be alleviated by aiding transesterification with alternative energy sources, i.e. ultrasound (US). In this study, biodiesel was obtained from Camelina sativa oil, aided with an ultrasonic probe (20kHz, 70% duty cycle, 50% amplitude). Design of experiments included the combination of sonication and agitation cycles, w/wo heating (50°C). To gain knowledge about the implications of the proposed methodology, conventional transesterification was optimized, resulting in higher needs on catalyst concentration and reaction time, compared to the proposed reaction. Although FAME content met EN 14103 standard, FAME yields were lower than those provided by US-assisted transesterification. Energy consumption measurements showed that ultrasound assisted transesterification required lower energy, temperature, catalyst and reaction time.

Insight into microwave-assisted lipase catalyzed synthesis of geranyl cinnamate: optimization and kinetic modeling.

Cinnamate esters have gained importance due to their unique antioxidant, flavor, and fragrance properties. Synergism of microwave irradiation and enzyme catalysis was investigated in transesterification of ethyl cinnamate and geraniol. Effects of different operating parameters such as biocatalyst, solvent, and temperature were first studied. An increase in initial rates up to 4.2-fold was observed under microwave irradiation vis-a-vis conventional heating. Further, the Taguchi L16 (4*4) orthogonal array design with four level-four variables and 16 run was employed for the optimization of parameters including enzyme loading, temperature, speed of agitation, and substrate mole ratio. Optimal conditions obtained via the Taguchi approach were as follows: enzyme loading, 60 mg; temperature, 65 °C; speed of agitation, 300 rpm; and substrate mole ratio, 1:2. The analysis of initial rate data established the validity of the ternary complex ordered bi-bi mechanism with inhibition by geraniol. The experimental data fitted very well with the model predictions.

Biodiesel from wet microalgae: extraction with hexane after the microwave-assisted transesterification of lipids.

A chloroform-free novel process for the efficient production of biodiesel from wet microalgae is proposed. Crude biodiesel is produced through extraction with hexane after microwave-assisted transesterification (EHMT) of lipids in wet microalgae. Effects of different parameters, including reaction temperature, reaction time, methanol dosage, and catalyst dosage, on fatty acids methyl esters (FAMEs) yield are investigated. The yield of FAME extracted into the hexane from the wet microalgae is increased 6-fold after the transesterification of lipids. The yield of FAME obtained through EHMT of lipids in wet microalgae is comparable to that obtained through direct transesterification of dried microalgae biomass with chloroform; however, FAME content in crude biodiesel obtained through EHMT is 86.74%, while that in crude biodiesel obtained through the chloroform-based process is 75.93%. EHMT ensures that polar pigments present in microalgae are not extracted into crude biodiesel, which leads to a 50% reduction in nitrogen content in crude biodiesel.

Key role of temperature monitoring in interpretation of microwave effect on transesterification and esterification reactions for biodiesel production.

Microwave effects have been quantified, comparing activation energies and pre-exponential factors to those obtained in a conventionally-heated reactor for biodiesel production from waste cooking oils via transesterification and esterification reactions. Several publications report an enhancement of biodiesel production using microwaves, however recent reviews highlight poor temperature measurements in microwave reactors give misleading reaction performances. Operating conditions have therefore been carefully chosen to investigate non-thermal microwave effects alone. Temperature is monitored by an optical fiber sensor, which is more accurate than infrared sensors. For the transesterification reaction, the activation energy is 37.1kJ/mol (20.1-54.2kJ/mol) in the microwave-heated reactor compared with 31.6kJ/mol (14.6-48.7kJ/mol) in the conventionally-heated reactor. For the esterification reaction, the activation energy is 45.4kJ/mol (31.8-58.9kJ/mol) for the microwave-heated reactor compared with 56.1kJ/mol (55.7-56.4kJ/mol) for conventionally-heated reactor. The results confirm the absence of non-thermal microwave effects for homogenous-catalyzed reactions.

Hybrid response surface methodology-genetic algorithm optimization of ultrasound-assisted transesterification of waste oil catalysed by immobilized lipase on mesoporous silica/iron oxide magnetic core-shell nanoparticles.

The production ofbiodiesel by transesterification of waste cooking oil (WCO) to partially substitute petroleum diesel is one of the measures for solving the twin problems of environment pollution and energy demand. An environmentally benign process for the enzymatic transesterification using immobilized lipase has attracted considerable attention for biodiesel production. Here, a superparamagnetic, high surface area substrate for lipase immobilization is evaluated. These immobilization substrates are composed of mesoporous silica/superparamagnetic iron oxide core-shell nanoparticles. The effects of methanol ratio to WCO, lipase concentration, water content and reaction time on the synthesis of biodiesel were analysed by utilizing the response surface methodology (RSM). A quadratic response surface equation for calculating fatty acid methyl ester (FAME) content as the objective function was established based on experimental data obtained in accordance with the central composite design. The RSM-based model was then used as the fitness function for genetic algorithm (GA) to optimize its input space. Hybrid RSM-GA predicted the maximum FAME content (91%) at the optimum level of medium variables: methanol ratio to WCO, 4.34; lipase content, 43.6%; water content, 10.22%; and reaction time, 6h. Moreover, the immobilized lipase could be used for four times without considerable loss of the activity.

Nonthermal effect of microwave irradiation in nonaqueous enzymatic esterification.

Microwave has nonthermal effects on enzymatic reactions, mainly caused by the polarities of the solvents and substrates. In this experiment, a model reaction with caprylic acid and butanol that was catalyzed by lipase from Mucor miehei in alkanes or arenes was employed to investigate the nonthermal effect in nonaqueous enzymatic esterification. With the comparison of the esterification carried by conventional heating and consecutive microwave irradiation, the positive nonthermal effect on the initial reaction rates was found substrate concentration-dependent and could be vanished ostensibly when the substrate concentration was over 2.0 mol L(-1). The polar parameter log P well correlates the solvent polarity with the microwave effect, comparing to dielectric constant and assayed solvatochromic solvent polarity parameters. The log P rule presented in conventional heating-enzymatic esterification still fits in the microwaved enzymatic esterification. Alkanes or arenes with higher log P provided positive nonthermal effect in the range of 2 ≤ log P ≤ 4, but yielded a dramatic decrement after log P = 4. Isomers of same log P with higher dielectric constant received stronger positive nonthermal effect. With lower substrate concentration, the total log P of the reaction mixture has no obvious functional relation with the microwave effect.

Ultrasound-assisted lipase-catalyzed transesterification of soybean oil in organic solvent system.

This work reports the transesterification of soybean oil with ethanol using two commercial immobilized lipases under the influence of ultrasound irradiation. The experiments were performed in an ultrasonic water bath, following a sequence of experimental designs to assess the effects of temperature, enzyme and water concentrations, oil to ethanol molar ratio and output irradiation power on the reaction yield. Results show that ultrasound-assisted lipase-catalyzed transesterification of soybean oil with ethanol might be a potential alternative route to conventional alkali-catalyzed method, as high reaction yields (~90 wt.%) were obtained at mild irradiation power supply (~100 W), and temperature (60 °C) in a relatively short reaction time, 4h, using Lipozyme RM IM as catalyst. The repeated use of the catalyst under the optimum experimental condition resulted in a decay in both enzyme activity and product conversion after two cycles. The use of Novozym 435 led to lower conversions (about 57%) but the enzyme activity was stable after eight cycles of use, showing, however, a reduction in product conversion after the forth cycle.

Multiphysics numerical modeling of the continuous flow microwave-assisted transesterification process.

Use of advanced microwave technology for biodiesel production from vegetable oil is a relatively new technology. Microwave dielectric heating increases the process efficiency and reduces reaction time. Microwave heating depends on various factors such as material properties (dielectric and thermo-physical), frequency of operation and system design. Although lab scale results are promising, it is important to study these parameters and optimize the process before scaling up. Numerical modeling approach can be applied for predicting heating and temperature profiles including at larger scale. The process can be studied for optimization without actually performing the experiments, reducing the amount of experimental work required. A basic numerical model of continuous electromagnetic heating of biodiesel precursors was developed. A finite element model was built using COMSOL Multiphysics 4.2 software by coupling the electromagnetic problem with the fluid flow and heat transfer problem. Chemical reaction was not taken into account. Material dielectric properties were obtained experimentally, while the thermal properties were obtained from the literature (all the properties were temperature dependent). The model was tested for the two different power levels 4000 W and 4700 W at a constant flow rate of 840ml/min. The electric field, electromagnetic power density flow and temperature profiles were studied. Resulting temperature profiles were validated by comparing to the temperatures obtained at specific locations from the experiment. The results obtained were in good agreement with the experimental data.

Enzymatic transesterification of Jatropha curcas oil assisted by ultrasonication.

Ultrasonication used for the production of fatty acid methyl ester from non-edible vegetable oil using immobilized lipase (Chromobacterium viscosum) as a catalyst from Enterobacter aerogenes to make the process fully ecologically and environmental friendly. The optimal conditions for biodiesel production is the molar ratio oil to methanol 1:4, catalyst concentration 5 wt.% of oil, reaction time 30 min, ultrasonic amplitude 50% (100 W/m(3)) and cycle 0.7s. ultrasonication reduce the reaction time comparing to the conventional batch process. The purity and conversion of the biodiesel was 84.5±0.5 analyzed by reversed phase HPLC.

Ultrasound-assisted third-liquid phase-transfer catalyzed esterification of sodium salicylate in a continuous two-phase-flow reactor.

The esterification of sodium salicylate to synthesize butyl salicylate by third-liquid phase-transfer catalysis under ultrasound irradiation was investigated in a continuous two-phase-flow reactor. The reactor was designed to keep the third-liquid phase in the middle part and to have the aqueous and organic phases flowing through it in countercurrent. Using tetra-n-butylphosphonium bromide to prepare the third-liquid phase for this esterification, the product yield in the organic outlet (toluene) at 70 degrees C was 49.7% in silent condition, showing the reaction promoted simply by countercurrent mixing of the aqueous and organic phases. In the conditions of space time at 168 min, stirring at 150 rpm and ultrasound irradiation (28 kHz, 300 W), the product yield was greatly enhanced to 78.2%. As prepared, above 90% of the added catalyst existed in the third-liquid phase, and after 4-h on stream for a large excess of n-butyl bromide to sodium salicylate, the fraction of catalyst retaining in the reactor was reduced to around 80%. The distributions of catalysts between phases before and after reaction were analyzed. A kinetic model was proposed to estimate the apparent rate constants, and the feasibility for third-liquid phase-transfer catalysis assisted by ultrasound irradiation in a continuous flow reactor was demonstrated.

Highly efficient esterification of ferulic acid under microwave irradiation.

A highly efficient synthesis of alkyl ferulates under microwave irradiation is described. The time of these reactions ranged from 3 to 5 minutes, which was much shorter than the traditional synthetic methods, and the alkyl ferulates were obtained in higher yields.

[Investigation on low power microwave irradiation-assisted enzymatic esterification in organic solvent by fluorescence spectroscopy].

The authors studied the fluorescence change of immobilized lipase from Rhizomucor miehei in the microwave assisted enzymatic esterification of caprylic acid and butanol in organic medium by investigating the fluorescence spectra in solvent or aqueous buffer after incubating the lipase with the solvent, caprylic acid and butanol under microwave irradiation, respectively. A comparison was made with the conventional heated enzymatic esterification in the solvents. Both of the heating modes, the microwave irradiation and conventional heating, can enhance the fluorescence intensity without shifting the emission wavelength of the lipase. In the circumstance that the irradiation can accelerate the esterification, the irradiation can enhance the exposure of the lipase protein molecules in the aqueous environment after incubating the lipase with solvents or the substrates. The effect of the reaction mixture on the fluorescence intensity was dominated by the solvents. The trend of the plot of log P versus the initial reaction rate was similar to that of log P versus fluorescence intensity of lipase in aqueous buffer after esterification; but was different from that of log P versus fluorescence intensity of lipase in organic medium.

Methoxyl groups of plant pectin as a precursor of atmospheric methane: evidence from deuterium labelling studies.

* The observation that plants produce methane (CH4) under aerobic conditions has caused considerable controversy among the scientific community and the general public. It led to much discussion and debate not only about its contribution to the global CH4 budget but also about the authenticity of the observation itself. Previous results suggested that methoxyl groups of the abundant plant structural component pectin might play a key role in the in situ formation process of CH4. Here, this effect is investigated using an isotope labelling study. * Polysaccharides, pectin and polygalacturonic acid, with varying degrees of trideuterium-labelled methyl groups in the methoxyl moieties, were investigated for CH4 formation under UV irradiation and heating. * A strong deuterium signal in the emitted CH4 was observed from these labelled polysaccharides. * Results clearly demonstrate that ester methyl groups of pectin can serve as a precursor of CH4, supporting the idea of a novel chemical route of CH4 formation in plants under oxic environmental conditions.

Ultrasound accelerated esterification of palmitic acid with vitamin C.

The esterification of palmitic acid with vitamin C in the presence of concentrated sulfuric acid as the solvent and catalyst by means of 25 kHz ultrasonic irradiation to obtain l-ascorbyl 6-palmitate is studied. By using ultrasound the dissolution rate of the reactants can be accelerated greatly, the reaction time of esterification can be reduced from 36 to 2h, and better yield (90-93%) of ester can be given by using 95% concentrated sulfuric acid as the solvent and catalyst, contrast to the yield of 75-85% by using 99% concentrated sulfuric acid without ultrasound. The influence of reaction conditions and ultrasonic parameters to the yield of ascorbyl palmitate are reported.

Efficient microwave assisted access to chiral O-(alpha-protected-aminoacyl)steroids.

Chiral O-(alpha-protected-aminoacyl)steroids 4a-f, 6a-b, 8 and 4a+4d and O-(alpha-protected-dipeptidoyl)steroids 12a,b are conveniently prepared under microwave irradiation in isolated yields of 65-96%, with complete chirality retention. The reaction utilized readily available N-(Z-alpha-aminoacyl)benzotriazoles 2a-f and Z-dipeptidoylbenzotriazole 11, with naturally occurring steroidal alcohols 3,5,7,9.

Enzymatic modification of cassava starch by bacterial lipase.

Enzymatic modification of starch using long chain fatty acid makes it thermoplastic suitable for a myriad of industrial applications. An industrial lipase preparation produced by Burkholderia cepacia (lipase PS) was used for modification of cassava starch with two acyl donors, lauric acid and palmitic acid. Reactions performed with palmitic acid by liquid-state and microwave esterification gave a degree of substitution (DS) of 62.08% (DS 1.45) and 42.06% (DS 0.98), respectively. Thermogravimetric analysis showed that onset of decomposition is at a higher temperature (above 600 degrees Celsius) for modified starch than the unmodified starch (280 degrees Celsius). Modified starch showed reduction in alpha-amylase digestibility compared to native starch (76.5-18%). Swelling power lowered for modified starch as esterification renders starch more hydrophobic, making it suitable for biomedical applications as materials for bone fixation and replacements, carriers for controlled release of drugs and bioactive agents. Thus enzymatic esterification is ecofriendly.

The formation of chlorophyll from chlorophyllide in leaves containing proplastids is a four-step process.

The time course of the different esters of chlorophyllide (Chlide) during the formation of chlorophyll a (Chl) in embryonic bean leaves containing proplastids was investigated by HPLC. After the reduction of photoactive Pchlide (Pchlide) to Chlide, three intermediates, i.e. Chlide geranylgeraniol, Chlide dihydrogeranylgeraniol and Chlide tetrahydrogeranylgeraniol were detected before the formation of Chlide phytol, i.e. authentic Chl. The transformation of Chlide to Chl was found to be much faster in leaves containing proplastids than in etiolated leaves with etioplasts.