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1.
The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound–enhanced biodiesel synthesis with the base–catalyst of CaO. A statistical design of experiments (Box–Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature = 62 °C, molar ratio = 10:1 and catalyst loading = 6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis–à–vis simulations of cavitation bubble dynamics. Due to 3–phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro–streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter–dependent.  相似文献   

2.
Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H2SO4) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)2) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)2 concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step.  相似文献   

3.
Investigation into newer routes of biodiesel synthesis is a key research area especially due to the fluctuations in the conventional fuel prices and the environmental advantages of biodiesel. The present work illustrates the use of sonochemical reactors for the synthesis of biodiesel from waste cooking oil. Transesterification of used frying oil with methanol, in the presence of potassium hydroxide as a catalyst has been investigated using low frequency ultrasonic reactor (20 kHz). Effect of different operating parameters such as alcohol–oil molar ratio, catalyst concentration, temperature, power, pulse and horn position on the extent of conversion of oil have been investigated. The optimum conditions for the transesterification process have been obtained as molar ratio of alcohol to oil as 6:1, catalyst concentration of 1 wt.%, temperature as 45 °C and ultrasound power as 200 W with an irradiation time of 40 min. The efficacy of using ultrasound has been compared with the conventional stirring approach based on the use of a six blade turbine with diameter of 1.5 cm operating at 1000 rpm. Also the purification aspects of the final product have been investigated.  相似文献   

4.
Microwave and ultrasound have been demonstrated to be outstanding process intensification techniques for transesterification of oil. According to their mechanisms, simultaneous effects can surely bring about better enhancement than sole microwave or ultrasound. Therefore, this study aimed to investigate the important factors and their suitable levels in the KOH-catalyzed transesterification of soybean oil with methanol by using synergistic assistance of microwave-ultrasound (CAMU). The feasibility of application of CAMU in transesterification of oil was demonstrated. When the dosage of methanol, soybean oil and KOH were 15.4 g, 34.7 g (with methanol-to-oil molar ratio of 12:1) and 1 g, respectively, and the microwave power, ultrasonic power, ultrasonic mode, reaction temperature and reaction time were 700 W, 800 W, 1:0, 65 °C and 6 min, respectively, the transesterification reached 98.0% of yield, being the highest yield among all the results obtained; while by using 600 W of microwave plus stirring instead of CAMU, only 57.4% of yield could be obtained. Compared with other reaction techniques, the transesterification by applying novel CAMU was found to have remarkable advantages. Furthermore, by monitoring the variation of real-time temperature and microwave power during transesterification reactions with different microwave operation time and by taking comparison of the corresponding yield, it was demonstrated that the main reason for the acceleration of microwave-assisted transesterification was the polarization and further activation of reactants caused by microwave irradiation, but not the factor of fast heating.  相似文献   

5.
《Ultrasonics sonochemistry》2014,21(5):1618-1623
Limited resources of conventional fuels such as petrodiesel have led to the search for alternative fuels. Various convention batch/continuous processes for the biodiesel production have been developed before the recent year. All processes are time consuming with high labor cost. Thus, we need a new process for biodiesel production which reduces the reaction time and production cost as well as save the energy. In this work, ultrasonic assisted transesterification of Jatropha curcas oil is carried out in the presence of methanol and potassium hydroxide (KOH) as catalyst, keeping the molar ratio of oil to alcohol 1:5, catalyst concentration 0.75 wt% of oil, ultrasonic amplitude 50% and pulse 0.3 cycle, 7 min reaction time under atmospheric condition. Ultrasonic mixing has increased the rate of transesterification reaction as compare to the mechanical mixing.  相似文献   

6.
Biodiesel production via esterification/transesterification reactions can be catalyzed by homogenous or heterogeneous catalysts. Development of heterogeneous catalysts for biodiesel production is highly advantageous due to the ease of product purification and of catalyst recyclability. In this current work, a novel acidic [DABCODBS][CF3SO3]2 dicationic ionic liquid (DIL) was used as heterogeneous catalyst to produce biodiesel using oleic acid as model oil. The esterification was conducted under ultrasonic irradiation (20 kHz) using a 14 mm ultrasonic horn transducer operated at various duty cycles. It was observed that the duty cycle, amplitude, methanol to oil molar ratio, catalyst amount and reaction temperature were the major factors that greatly impact the necessary reaction time to lead to a high yield of biodiesel. The reaction conditions were optimized with the aid of Response Surface Methodology (RSM) designed according to the Quadratic model of the Box Behnken method. The optimum conditions were found to be at catalyst amount of 0.64 mol%, methanol to oil ratio of 14.3:1, temperature of 59 °C, reaction time of 83 min and amplitude of 60% in continuous mode. The results showed that the oleic acid was successfully converted into esters with conversion value of 93.20% together with significant reduction of reaction time from 7 h (using mechanical stirring) to 83 min (using ultrasonication). The results also showed that the acidic DIL catalyst we designed purposely was efficient to catalyze the ultrasonic-assisted esterification yielding high conversion of oleic acid to methyl oleate on short times. The DIL was also recycled and reused for at least five times without significant reduction in performance. Overall, the procedure offers advantages including short reaction time, good yield, operational simplicity and environmentally benign characteristics.  相似文献   

7.
This study demonstrates the potential of Na-silica waste sponge as a source of low cost catalyst in the transesterification of waste cooking oil aided by ultrasound. In this work an environmentally friendly and efficient transesterification process using Na-loaded SiO2 from waste sponge skeletons as a solid catalyst is presented. The results showed that the methyl esters content of 98.4 ± 0.4 wt.% was obtainable in less than an hour (h) of reaction time at 55 °C. Optimization of reaction parameters revealed that MeOH:oil, 9:1; catalyst, 3 wt.% and reaction duration of 30 min as optimum reaction conditions. The catalyst is able to tolerant free fatty acid and moisture content up to 6% and 8%, respectively. In addition, the catalyst can be reused for seven cycles while maintaining the methyl esters content at 86.3%. Ultrasound undoubtedly assisted in achieving this remarkable result in less than 1 h reaction time. For the kinetics study at 50–60 °C, a pseudo first order model was proposed, and the activation energy of the reaction is determined as 33.45 kJ/mol using Arrhenius equation.  相似文献   

8.
The present work demonstrates the application of a hydrodynamic cavitation reactor for the synthesis of biodiesel with used frying oil as a feedstock. The synthesis involved the transesterification of used frying oil (UFO) with methanol in the presence of potassium hydroxide as a catalyst. The effect of geometry and upstream pressure of a cavitating orifice plate on the rate of transesterification reaction has been studied. It is observed that the micro level turbulence created by hydrodynamic cavitation somewhat overcomes the mass transfer limitations for triphasic transesterification reaction. The significant effects of upstream pressure on the rate of formation of methyl esters have been seen. It has been observed that flow geometry of orifice plate plays a crucial role in process intensification. With an optimized plate geometry of 2 mm hole diameter and 25 holes, more than 95% of triglycerides have been converted to methyl esters in 10 min of reaction time with cavitational yield of 1.28 × 10?3 (Grams of methyl esters produced per Joule of energy supplied). The potential of UFO to produce good quality methyl esters has been demonstrated.  相似文献   

9.
The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.  相似文献   

10.
The present work demonstrates the hydrolysis of waste cooking oil (WCO) under solvent free condition using commercial available immobilized lipase (Novozyme 435) under the influence of ultrasound irradiation. The process parameters were optimized using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound intensity. It has been observed that ultrasound-assisted lipase-catalyzed hydrolysis of WCO would be a promising alternative for conventional methods. A maximum conversion of 75.19% was obtained at mild operating parameters: molar ratio of oil to water (buffer pH 7) 3:1, catalyst loading of 1.25% (w/w), lower ultrasound power 100 W (ultrasound intensity – 7356.68 W m−2), duty cycle 50% and temperature (50 °C) in a relatively short reaction time (2 h). The activation energy and thermodynamic study shows that the hydrolysis reaction is more feasible when ultrasound is combined with mechanical agitation as compared with the ultrasound alone and simple conventional stirring technique. Application of ultrasound considerably reduced the reaction time as compared to conventional reaction. The successive use of the catalyst for repetitive cycles under the optimum experimental conditions resulted in a loss of enzymatic activity and also minimized the product conversion.  相似文献   

11.
Ultrasound assisted intensification of synthesis of biodiesel from waste cooking oil using methyl acetate and immobilized lipase obtained from Thermomyces lanuginosus (Lipozyme TLIM) as a catalyst has been investigated in the present work. The reaction has also been investigated using the conventional approach based on stirring so as to establish the beneficial effects obtained due to the use of ultrasound. Effect of operating conditions such as reactant molar ratio (oil and methyl acetate), temperature and enzyme loading on the yield of biodiesel has been investigated. Optimum conditions for the conventional approach (without ultrasound) were established as reactant molar ratio of 1:12 (oil:methyl acetate), enzyme loading of 6% (w/v), temperature of 40 °C and reaction time of 24 h and under these conditions, 90.1% biodiesel yield was obtained. The optimum conditions for the ultrasound assisted approach were oil to methyl acetate molar ratio of 1:9, enzyme loading of 3% (w/v), and reaction time of 3 h and the biodiesel yield obtained under these conditions was 96.1%. Use of ultrasound resulted in significant reduction in the reaction time with higher yields and lower requirement of the enzyme loading. The obtained results have clearly established that ultrasound assisted interesterification was a fast and efficient approach for biodiesel production giving significant benefits, which can help in reducing the costs of production. Reusability studies for the enzyme were also performed but it was observed that reuse of the catalyst under the optimum experimental condition resulted in reduced enzyme activity and biodiesel yield.  相似文献   

12.
In the present work, high speed homogenizer has been used for the intensification of biodiesel synthesis from soybean oil and waste cooking oil (WCO) used as a sustainable feedstock. High acid value waste cooking oil (27 mg of KOH/g of oil) was first esterified with methanol using sulphuric acid as catalyst in two stages to bring the acid value to desired value of 1.5 mg of KOH/g of oil. Transesterification of soybean oil (directly due to lower acid value) and esterified waste cooking oil was performed in the presence of heterogeneous catalyst (CaO) for the production of biodiesel. Various experiments were performed for understanding the effect of operating parameters viz. molar ratio, catalyst loading, reaction temperature and speed of rotation of the homogenizer. For soybean oil, the maximum biodiesel yield as 84% was obtained with catalyst loading of 3 wt% and molar ratio of oil to methanol of 1:10 at 50 °C with 12,000 rpm as the speed of rotation in 30 min. Similarly biodiesel yield of 88% was obtained from waste cooking oil under identical operating conditions except for the catalyst loading which was 1 wt%. Significant increase in the rate of biodiesel production with yields from soybean oil as 84% (in 30 min) and from WCO as 88% (30 min) was established due to the use of high speed homogenizer as compared to the conventional stirring method (requiring 2–3 h for obtaining similar biodiesel yield). The observed intensification was attributed to the turbulence caused at microscale and generation of fine emulsions due to the cavitational effects. Overall it can be concluded from this study that high speed homogenizer can be used as an alternate cavitating device to efficiently produce biodiesel in the presence of heterogeneous catalysts.  相似文献   

13.
Sucrose fatty acid esters were synthesized by the transesterification of sucrose with aliphatic esters under ultrasound irradiation in good yield (?73%). The optimum reaction conditions for the transesterification reaction include a molar ratio of sucrose to fatty acid ethyl ester of 2:1 and the use of a 13% mol anhydrous K2CO3 catalyst. The optimum reaction temperature was set at 70 °C, the optimum reaction time was 2 h, and the optimum reaction pressure was 11 kPa. The reaction had excellent monoester selectivity. The proportion of monoester (6-monoester + 6′-monoester) in the purified products was up to 92–95% via flash column chromatography over silica gel, the ratios of 6-monoester/6′-monoester are 2.1–2.7, and the sucrose monoesters were identified by HPLC–MS, NMR and IR.  相似文献   

14.
Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is a significant reaction for obtaining industrially important products. The current research work deals with intensification of reaction of 4-bromoanisole and phenylboronic acid catalyzed with 5 wt% Pd/C (5% by weight Pd supported on C available as commercial catalyst) using ultrasound and more importantly, without use of any additional phase transfer catalyst. Heterogeneous catalyst has been selected in the present work so as to harness the benefits of easy separation and the possible limitations of heterogeneous operation are minimized by introducing ultrasonic irradiations. The effect of operating parameters such as ultrasound power, temperature, catalyst loading and molar ratio on the progress of reaction has been investigated. It has been observed that an optimum power, temperature and catalyst loading exist for maximum benefits whereas higher molar ratio was found to be favourable for the progress of the reaction. Also, the use of ultrasound reduced the reaction time from 70 min required in conventional approach to only 35 min under conditions of frequency of 22 kHz, power dissipation of 40 W and catalyst loading as 1.5 mol% (refers to total quantum of catalyst used in the work) in ethanol-water system under ambient conditions. The work also demonstrated successful results at ten times higher volume as compared to the normally used volumes in the case of simple ultrasonic horn. Overall, the work has successfully demonstrated process intensification benefits obtained due to the use of ultrasound for heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction.  相似文献   

15.
《Ultrasonics sonochemistry》2014,21(4):1374-1381
Conventional and ultrasound-assisted hydrolysis and subsequent esterification of Nagchampa oil under mild operating conditions have been investigated with an objective of intensification of methyl esters production using a sustainable approach. The effect of ratio of reactants, temperature, enzyme loading, pretreatment of enzyme (using ultrasonic irradiations) on the hydrolysis and esterification reaction has been studied. Optimum conditions for hydrolysis were observed to be 1:1 weight ratio of oil: water for Lip Z and 1:3 for Lip 2 enzymes, enzyme loading of 400 units for Lip Z and 800 mg for Lip 2 enzymes and reaction time of 6 h. In the case of esterification reaction, optimum conditions obtained were oil to methanol molar ratio of 1:2, enzyme loading of 1000 mg and reaction time of 20 h. Use of pretreated enzyme (using ultrasonic irradiations) was found to increase the extent of esterification reaction from 75% to 92.5%. It was observed that use of ultrasound in the reaction significantly intensified the esterification reaction with time requirement reducing from 20 h for conventional stirring based approach to only about 7.5 h in the presence of ultrasound. The extent of esterification obtained with sonicated enzyme also increased to 96% from 75% with unsonicated enzyme.  相似文献   

16.
The catalytic esterification of sodium 4-hydroxybenzoate with benzyl bromide by ultrasound-assisted solid–liquid phase-transfer catalysis (U-SLPTC) was investigated using the novel dual-site phase-transfer catalyst 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl dichloride (BTBAMBC), which was synthesized from the reaction of 4,4′-bis(chloromethyl)-1,1′-biphenyl and tributylamine. Without catalyst and in the absence of water, the product yield at 60 °C was only 0.36% in 30 min of reaction even under ultrasound irradiation (28 kHz/300 W) and 250 rpm of stirring speed. When 1 cm3 of water and 0.5 mmol of BTBAMBC were added, the yield increased to 84.3%. The catalytic intermediate 4,4′-bis(tributylammoniomethyl)-1,1′-biphenyl di-4-hydroxybenzoate was also synthesized to verify the intrinsic reaction which was mainly conducted in the quasi-aqueous phase locating between solid and organic phases. Pseudo-first-order kinetic equation was used to correlate the overall reaction, and the apparent rate coefficient with ultrasound (28 kHz/300 W) was 0.1057 min−1, with 88% higher than that (0.0563 min−1) without ultrasound. The esterification under ultrasonic irradiation using BTBAMBC by solid–liquid phase-transfer catalysis was developed.  相似文献   

17.
In this work, high frequency and low power ultrasound without external heating source and mechanical stirring in biodiesel production were studied. Transesterification of soybean oil with methanol and catalyzed by KOH was investigated using ultrasound equipment and ultrasonic transducer. The effect of ultrasonic output power (3 W–9 W), ultrasonic frequency (1 MHz and 3 MHz), and alcohol to oil molar ratio (6:1 and 8:1) have been investigated. The increase in ultrasonic power provided higher conversion rates. In addition, higher conversion rates were obtained by increasing the ultrasonic frequency from 1 MHz to 3 MHz (48.7% to 79.5%) for the same reaction time. Results also indicate that the speed of sound can be used to evaluate the produced biodiesel qualitatively. Further, the ultrasound system presented electric consumption (46.2 W∙h) four times lower than achieved using the conventional method (211.7 W∙h and 212.3 W∙h). Thus, biodiesel production using low power ultrasound in the MHz frequency range is a promising technology that could contribute to biodiesel production processes.  相似文献   

18.
The influence of low-frequency ultrasound (40 kHz) in the esterification reaction between acetic acid and butanol for flavor ester synthesis catalyzed by the commercial immobilized lipase B from Candida antarctica (Novozym 435) was evaluated. A central composite design and the response surface methodology were used to analyze the effects of the reaction parameters (temperature, substrate molar ratio, enzyme content and added water) and their response (yields of conversion in 2.5 h of reaction). The reaction was carried out using n-hexane as solvent. The optimal conditions for ultrasound-assisted butyl acetate synthesis were found to be: temperature of 46 °C; substrate molar ratio of 3.6:1 butanol:acetic acid; enzyme content of 7%; added water of 0.25%, conditions that are slightly different from those found using mechanical mixing. Over 94% of conversion was obtained in 2.5 h under these conditions. The optimal acid concentration for the reaction was determined to be 2.0 M, compared to 0.3 M without ultrasound treatment. Enzyme productivity was significantly improved to around 7.5-fold for each batch when comparing ultrasound and standard mechanical agitation. The biocatalyst could be directly reused for 14 reactions cycles keeping around 70% of its original activity, while activity was virtually zeroed in the third cycle using the standard mixing system. Thus, compared to the traditional mechanical agitation, ultrasound technology not only improves the process productivity, but also enhances enzyme recycling and stability in the presence of acetic acid, being a powerful tool to improve biocatalyst performance in this type of reaction.  相似文献   

19.
《Ultrasonics sonochemistry》2014,21(5):1752-1762
The aim of this study is to investigate modified TiO2 doped with C4H4O6HK as heterogeneous solid base catalyst for transesterification of non-edible, Silybum marianum oil to biodiesel using methanol under ultrasonication. Upon screening the catalytic performance of modified TiO2 doped with different K-compounds, 0.7 C4H4O6HK doped on TiO2 was selected. The preparation of the catalyst was done using incipient wetness impregnation method. Having doped modified TiO2 with C4H4O6HK, followed by impregnation, drying and calcination at 600 °C for 6 h, the catalyst was characterized by XRD, FTIR, SEM, BET, TGA, UV and the Hammett indicators. The yield of the biodiesel was proportional to the catalyst basicity. The catalyst had granular and porous structures with high basicity and superior performance. Combined conditions of 16:1 molar ratio of methanol to oil, 5 wt.% catalyst amount, 60 °C reaction temperature and 30 min reaction time was enough for maximum yield of 90.1%. The catalyst maintained sustained activity after five cycles of use. The oxidative stability which was the main problem of the biodiesel was improved from 2.0 h to 3.2 h after 30 days using ascorbic acid as antioxidant. The other properties including the flash point, cetane number and the cold flow ones were however, comparable to international standards. The study indicated that Ti-0.7-600-6 is an efficient, economical and environmentally, friendly catalyst under ultrasonication for producing biodiesel from S. marianum oil with a substantial yield.  相似文献   

20.
The production of biodiesel from non-edible vegetable oil using ultrasonication, calls for an efficient solid catalyst to make the process fully ecologically and economically friendly. The methodology allows for the reaction to be run under atmospheric conditions. Solid catalyst and ultrasonication reduced the reaction time comparing to the conventional batch processes and we found 98.53% biodiesel yield. The optimal conditions for biodiesel production is the molar ratio oil to methanol 1:9, Catalyst conc. 3 wt.% of oil and 15 min reaction time.  相似文献   

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