High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the ...High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the transesterification of dimethyl carbonate(DMC)with ethylene glycol(EG)is provided in this work.However,this reaction is so fast that the reaction kinetics,which is essential for the industrial design,is hard to get by the traditional measuring method.In this work,an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst.The effects of flow rate,microreactor diameter,catalyst concentration,reaction temperature,and reactant molar ratio were investigated.An activity-based pseudohomogeneous kinetic model,which considered the non-ideal properties of reaction system,was established to describe the transesterification of DMC with EG.Detailed kinetics data were collected in the first 5 min.Using these data,the parameters of the kinetic model were correlated with the maximum average error of 11.19%.Using this kinetic model,the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%,suggesting its satisfactory prediction performance.展开更多
For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the proc...For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality.The present study aims at characterizing a well-known industrial process,the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters(FAME)for usage as biodiesel in a continuous micro reactor set-up.To this end,a design of experiment approach is applied,where the effects of two process factors,the molar ratio and the total flow rate of the reactants,are investigated.The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield.The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression.The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis.A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination(R^(2))of 0.9608.Thus,we applied a PAT approach to generate further insight into this established industrial process.展开更多
The catalytic performance of KOH/mordenite has been studied for transesterification of palm oil using a batch reactor and a packed-bed reactor at 60 C and atmospheric pressure.The KOH/mordenite processed transesterifi...The catalytic performance of KOH/mordenite has been studied for transesterification of palm oil using a batch reactor and a packed-bed reactor at 60 C and atmospheric pressure.The KOH/mordenite processed transesterification in the batch reactor gave the highest methyl ester yield of96.7%under optimum conditions,while a methyl ester content over 94.5%was obtained in the packed-bed reactor.This comparison indicates that transesterification in a batch-type reactor gives a higher methyl ester yield than that of a continuous-flow reactor.Dealumination was found in the calcined catalysts and had a significant effect on the physical structure and chemical composition of the catalysts.Leaching of the potassium species was negligible,whereas depositing and washing of the reacted mixture with acetone on the catalyst surface were observed by FTIR.展开更多
Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in...Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in acid-catalyzed reactions and elucidating the effects of the defects in UiO-66 materials on their catalytic performances, in this work, a series of zirconium-containing UiO-66 samples were synthesized by varying the synthesis temperatures and BDC/Zr(terephthalic acid/ZrCl) ratios in the synthesis system.The synthesized UiO-66 samples were characterized by X-ray diffraction(XRD), Nadsorption-desorption,scanning electron microscopy(SEM), thermogravimetrical analysis(TGA), temperature-programmed desorption of NH(NH-TPD). Their catalytic performances were investigated in transesterification of tributyrin and soybean oil with methanol. The results showed that UiO-66 samples with different amounts of defects could be successfully prepared by varying the synthesis temperatures and/or the BDC/Zr ratios used in the synthesis system. The catalytic activities of the UiO-66 materials greatly depended on their linker defects and enhanced with the increase of the defect amount. The UiO-66 was an efficient catalyst for transesterification of tributyrin and soybean oil with methanol under mild reaction conditions and its catalytic activity was comparable to other solid acid catalysts reported in the literatures. The UiO-66 catalyst was relatively stable and could be reused.展开更多
The transesterification reaction conditions of tung oil with methanol have been studied in this article, with immobilized lipase NOVO435 as catalyst. The response surface methodology was used to optimize the transeste...The transesterification reaction conditions of tung oil with methanol have been studied in this article, with immobilized lipase NOVO435 as catalyst. The response surface methodology was used to optimize the transesterification reaction of tung oil in a nonsolvent system. The optimal conditions were rotation rate 200 r/min, molar ratio of methanol to oil 2.2: l, reaction temperature 43℃, and the catalyst amount 14% (based on the weight of oil). After reacting for 18 h, 67.5% of the oil was converted to its corresponding methyl esters (the theoretical ester conversion was 73.3%). The lipase was washed by organic solvents after each reaction and was reused again. The esters conversion of tung oil was decreased by 6% after the lipase was reused for 120 h. The theoretical amount of methanol was added in two steps, 85% ester conversion was obtained after 36 h of reaction (theoretical ester conversion was 100%). The molar ratio of methanol to oil, the catalyst amount, the reaction temperature, and reaction time were all highly significant factors, and there was a relative significant interaction between every two factors.展开更多
The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and pheno...The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1.展开更多
The non-edible oils are believed to be one of the major feedstock for the production of biodiesel in future.In the present study,we investigated the production of Jatropha oil methyl esters(JOMEs) via alkali-catalyz...The non-edible oils are believed to be one of the major feedstock for the production of biodiesel in future.In the present study,we investigated the production of Jatropha oil methyl esters(JOMEs) via alkali-catalyzed transesterification route.The biophysical characteristics of Jatropha oil were found within the optimal range in accordance with ASTM standards as a substitute diesel fuel.The chemical composition and production yield of as-synthesized biodiesel were confirmed by various analytical techniques such as FT-IR,1H NMR,13 C NMR and gas chromatography coupled with mass spectrometry.A high percentage conversion,~96.09%,of fatty acids into esters was achieved under optimized transesterification conditions with 6 :1 oil to methanol ratio and 0.9 wt% Na OH for 50 min at ~60°C.Moreover,twelve fatty acids methyl esters(FAME) were quantified in the GC/MS analysis and it was interesting to note that the mass fragmentation pattern of saturated,monounsaturated and diunsaturated FAME was comparable with the literature reported values.展开更多
The transesterification of palm oil and methanol catalyzed by Br?nsted acidic ionic liquids was investigated. Four eco-friendly Br?nsted acidic ionic liquids were prepared and their structures were characterized by NM...The transesterification of palm oil and methanol catalyzed by Br?nsted acidic ionic liquids was investigated. Four eco-friendly Br?nsted acidic ionic liquids were prepared and their structures were characterized by NMR, FT-IR and TG–DTG. The results demonstrated that [CyN_(1,1)PrSO_3H][p-TSA] was more efficient than the other ionic liquids and chosen as catalyst for further research. The influences of various reaction parameters on the conversion of palm oil to biodiesel were performed, and the orthogonal test was investigated to seek the optimum reaction conditions, which were illustrated as follows: methanol to oil mole ratio of 24:1, catalyst dosage of 3.0 wt% of oil, reaction temperature of 120 °C, reaction time of 150 min, and the biodiesel yield achieved 98.4%. In addition, kinetic study was established for the conversion process, with activation energy and preexponential factor of 122.93 k J·mol^(-1) and 1.83 × 10^(15), respectively. Meanwhile, seven-time recycling runs of ionic liquid were completed with ignorable loss of its catalyst activity. The refined biodiesel met the biodiesel standard EN 14214.展开更多
The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influenc...The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influence on fluid mixing and oil conversion was investigated for a range of operating conditions: Reynolds number(Re = 0.1–100),Temperature(25–75 °C), ethanol/oil molar ratio(6-12), and catalyst concentration(0.75 wt%–1.25 wt%), using three microchannel configurations(Length = 35 mm; Width = 1500 μm; Height = 200 μm): T-shape – channel without obstructions; MCO – channel with 3 obstructions ensemble – equally disposed over longitudinal length;MWO – channel with 7 obstructions ensemble. The MCO micromixer was based on literature work, and the MWO is a totally new micromixer design. Experimental tests were conducted in similar conditions in microreactors using these micromixers(Length = 411 mm) made of polydimethylsiloxane. The MCO configuration presented the highest performance(mixing index of 0.80 at Re = 100), oil conversion of 81.13% at 75 °C, molar ratio of 9 and catalyst concentration of 1%. Experimental results showed high conversions for MCO and MWO configurations(99.99%) at 50 °C, molar ratio of 9 and catalyst concentration of 1%, with a residence time of 12 s.展开更多
The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol has been investigated. X-ray diffraction (XRD), X-ray pho...The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol has been investigated. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), thermogravimetry analysis (TG), atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterization. The results show that, the formation of Pb4O(OC6H5)6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead, which is the cause of the catalyst deactivation. In addition, the composition of the leached lead is ascertained to be a mixture of Pb4O(OC6H5)6 and PbO with the weight percentage of 62.7% and 37.3%, respectively.展开更多
Biodiesel is an alternative renewable fuel which is produced by using biomass resources. Its physicochemical properties are close to those of the petroleum diesel fuel. This study highlights biodiesel production from ...Biodiesel is an alternative renewable fuel which is produced by using biomass resources. Its physicochemical properties are close to those of the petroleum diesel fuel. This study highlights biodiesel production from safflower seed oil. The main aim of this experimental work is to optimize the process parameters, namely the methanolto-oil molar ratio, catalyst concentration, reaction time and reaction temperature for biodiesel production. The Taguchi robust design approach was used with an L9 orthogonal array to analyze the influence of process factors on performance parameters. The results showed that the optimum yield of biodiesel was 93.8% with viscosity 5.60 c St, with a methanol-to-oil molar ratio of 4:1, catalyst concentration of 1.5 wt%, reaction time of 90 min and reaction temperature of 60 ℃. The catalyst concentration was found to be the most influencing parameter which contributed 51.1% and 50.8% of the total effect on the yield of biodiesel, Y;, and viscosity of biodiesel, Y;, respectively.展开更多
Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1 ( 2.5 wt% Ti ) catalyst. TS-1 catalyst, as a heterogeneous catalyst, showed excellent selectivity of diphenyl oxalat...Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1 ( 2.5 wt% Ti ) catalyst. TS-1 catalyst, as a heterogeneous catalyst, showed excellent selectivity of diphenyl oxalate and methylphenyl oxalate compared with other homogeneous catalysts. Lewis acid sites on TS-1 catalyst were the active sites for transesterification of dimethyl oxalate with phenol. The high selectivity was closely related to the weak acid sites over TS-1.展开更多
It is hoped to develop a simple and low cost route for preparing the CaO with a novel morphology which can present high catalytic activity in catalyzing transesterification reaction for biodiesel. The porous CaO micro...It is hoped to develop a simple and low cost route for preparing the CaO with a novel morphology which can present high catalytic activity in catalyzing transesterification reaction for biodiesel. The porous CaO microsphere was synthesized by calcining spherical CaCO3 precursor which was prepared easily by mixing CaCl2 with Na2CO3. The as-prepared CaO microsphere was characterized by scanning electronic microscopy(SEM), powder X-ray diffractometry(XRD) and N2 adsorption experiment. The results reveal that the synthesized CaO is regular microsphere with many pores in its exterior and interior. The CaO microsphere is applied in catalyzing the transesterification reaction of soybean oil for biodiesel and presents excellent catalytic ability with a transesterification yield of 98.72%. This catalyst could have potential applications in other fields in view of its well-defined morphology, simply synthetic route and low cost.展开更多
A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 (CO3 )4 (OH)2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use o...A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 (CO3 )4 (OH)2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant. Reaction time has an important effect on the final morphology of the product. The micro-structure and morphology of Mg5 (CO3)4 (OH)2·4H2O were characterized by means of X-ray diffractometry (XRD), fieldemission scanning electron microscopy(FE-SEM). Brunauer-Emmett-Teller(BET) surface areas of the samples were also measured. The probable formation mechanism of flower-like micro-structure was discussed. It was found that Mg5 (CO3)4( OH)2·4H2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol.展开更多
Four ionic liquids [BMIM]OH, [BMIM]IM, [BMIM]Br, and [BMIM]PF6 were synthesized and characterized by infrared spectroscopy. Then the effects of ionic liquids(ILs), cocatalysts, and reaction temperature on the catalyti...Four ionic liquids [BMIM]OH, [BMIM]IM, [BMIM]Br, and [BMIM]PF6 were synthesized and characterized by infrared spectroscopy. Then the effects of ionic liquids(ILs), cocatalysts, and reaction temperature on the catalytic performance for transesterification of ethylene carbonate and methanol were investigated with orthogonal experiments. The influence of cations and anions of ILs on catalytic activity was revealed by the density functional theory(DFT). The reaction mechanism was proposed based on the experimental results and DFT. The results demonstrated that the optimal catalyst was [Bmim]PF6/CaO, which exhibited the advantages of high activity, excellent stability, and easy recycling. Under the optimized conditions covering a catalytic temperature of 130 °C, an ionic liquid/cocatalyst mass ratio of 5:1, and a catalyst dosage of 4.0%, the conversion rate could reach 65.23% with a dimethyl carbonate selectivity of 98.95%. No significant loss of catalyst activity was detected after 7 recycle times.展开更多
The synthesis of acyclovir and L-ascorbic acid with divinyladipate was performed with alkaline protease from Bacillus subtilis and lipase from Lipozyme (immobilized from Mucor miehei) in different anhydrous organic so...The synthesis of acyclovir and L-ascorbic acid with divinyladipate was performed with alkaline protease from Bacillus subtilis and lipase from Lipozyme (immobilized from Mucor miehei) in different anhydrous organic solvents. Two corresponding derivatives were obtained.展开更多
The transesterification of diphenyl carbonate (DPC) with 1,4-butyldiol (BD) was kinetically investigated in the presence of lithium acetate catalyst at 465 K.The reaction was followed by the measurement of the qua...The transesterification of diphenyl carbonate (DPC) with 1,4-butyldiol (BD) was kinetically investigated in the presence of lithium acetate catalyst at 465 K.The reaction was followed by the measurement of the quantity of phenol which was distilled from the reactor.The experiments supported the assumption that the phenyl ester groups in DPC and phenyl hdroxybutyl carbonate (PHBH) had the same reactivity,and the transesterification obeyed first-order kinetics with respect to DPC and BD,and a rate equation was derived.The reaction rate was found to be first order with respect to the catalyst concentration as well.When those data were incorporated in the rate equation,excellent agreement between calculated values and the observed ones was recognized over a wide range.展开更多
The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features ...The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features of these compounds were described, and the possible mechanism of the novel transesterification was suggested.展开更多
This research investigates the effect of reaction variables that strongly affect the cost of biodiesel production from non-edible Spirulina-Platensis microalgae lipids, and use the acid-catalyzed in situ transesterifi...This research investigates the effect of reaction variables that strongly affect the cost of biodiesel production from non-edible Spirulina-Platensis microalgae lipids, and use the acid-catalyzed in situ transesterification process. Experiments were designed to determine how variations in volume of reacting methanol, the concentration of an acid catalyst, time, temperature and stirring affected the biodiesel yield. The total lipid content of Spirulina-Platensis microalgae was obtained to be 0.1095g/g biomass. The weight of the by-product glycerol obtained was used to predict the percentage yield conversion of microalgae oil biodiesel. Best results (84.7%), a yield of fatty acid methyl ester (FAME), were obtained at 100% (wt./wt.oil) catalyst concentration, 80 ml methanol volumes, 8 h reaction time and 65℃ reaction temperature with continuous stirring at 650 rpm. Properties of the produced biodiesel were measured according to EN 14214 standards.展开更多
For transesterification of Jatropha oil into biodiesel, ultrasound assisted transesterification seems to be promising in terms of reduction in process time and stages of operation. Effects of process variables such as...For transesterification of Jatropha oil into biodiesel, ultrasound assisted transesterification seems to be promising in terms of reduction in process time and stages of operation. Effects of process variables such as the catalyst loading, the molar ratio of methanol to oil, reaction temperature and the reaction time were investigated on the conversion of Jatropha oil to biodiesel. The conversion was above 93% under the conditions of 50?C, methanol to oil molar ratio of 9:1, reaction time 30 min and catalyst amount (catalyst/oil) of 1% wt%. A kinetic study of transesterification of Jatropha oil based on ultrasound assisted synthesis is presented in this paper. Rate equation obtained is also presented.展开更多
基金support for this work from the National Natural Science Foundation of China(21706034)the Natural Science Foundation of Fujian Province(2021J01645)the Key Program of Qingyuan Innovation Laboratory(00221004).
文摘High-purity ethylene carbonate(EC)is widely used as battery electrolyte,polycarbonate monomer,organic intermediate,and so on.An economical and sustainable route to synthesize high-purity ethylene carbonate(EC)via the transesterification of dimethyl carbonate(DMC)with ethylene glycol(EG)is provided in this work.However,this reaction is so fast that the reaction kinetics,which is essential for the industrial design,is hard to get by the traditional measuring method.In this work,an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst.The effects of flow rate,microreactor diameter,catalyst concentration,reaction temperature,and reactant molar ratio were investigated.An activity-based pseudohomogeneous kinetic model,which considered the non-ideal properties of reaction system,was established to describe the transesterification of DMC with EG.Detailed kinetics data were collected in the first 5 min.Using these data,the parameters of the kinetic model were correlated with the maximum average error of 11.19%.Using this kinetic model,the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%,suggesting its satisfactory prediction performance.
文摘For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality.The present study aims at characterizing a well-known industrial process,the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters(FAME)for usage as biodiesel in a continuous micro reactor set-up.To this end,a design of experiment approach is applied,where the effects of two process factors,the molar ratio and the total flow rate of the reactants,are investigated.The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield.The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression.The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis.A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination(R^(2))of 0.9608.Thus,we applied a PAT approach to generate further insight into this established industrial process.
基金supported financially by the National Metal and Materials Technology Center,Thailandthe Center of Excellence on Petrochemical and Materials Technology,Thailand
文摘The catalytic performance of KOH/mordenite has been studied for transesterification of palm oil using a batch reactor and a packed-bed reactor at 60 C and atmospheric pressure.The KOH/mordenite processed transesterification in the batch reactor gave the highest methyl ester yield of96.7%under optimum conditions,while a methyl ester content over 94.5%was obtained in the packed-bed reactor.This comparison indicates that transesterification in a batch-type reactor gives a higher methyl ester yield than that of a continuous-flow reactor.Dealumination was found in the calcined catalysts and had a significant effect on the physical structure and chemical composition of the catalysts.Leaching of the potassium species was negligible,whereas depositing and washing of the reacted mixture with acetone on the catalyst surface were observed by FTIR.
基金supported by the National Science Foundation of China (Nos. 20971095 and 21576177)Research Project Supported by Shanxi Scholarship Council of China (2013-047)
文摘Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in acid-catalyzed reactions and elucidating the effects of the defects in UiO-66 materials on their catalytic performances, in this work, a series of zirconium-containing UiO-66 samples were synthesized by varying the synthesis temperatures and BDC/Zr(terephthalic acid/ZrCl) ratios in the synthesis system.The synthesized UiO-66 samples were characterized by X-ray diffraction(XRD), Nadsorption-desorption,scanning electron microscopy(SEM), thermogravimetrical analysis(TGA), temperature-programmed desorption of NH(NH-TPD). Their catalytic performances were investigated in transesterification of tributyrin and soybean oil with methanol. The results showed that UiO-66 samples with different amounts of defects could be successfully prepared by varying the synthesis temperatures and/or the BDC/Zr ratios used in the synthesis system. The catalytic activities of the UiO-66 materials greatly depended on their linker defects and enhanced with the increase of the defect amount. The UiO-66 was an efficient catalyst for transesterification of tributyrin and soybean oil with methanol under mild reaction conditions and its catalytic activity was comparable to other solid acid catalysts reported in the literatures. The UiO-66 catalyst was relatively stable and could be reused.
文摘The transesterification reaction conditions of tung oil with methanol have been studied in this article, with immobilized lipase NOVO435 as catalyst. The response surface methodology was used to optimize the transesterification reaction of tung oil in a nonsolvent system. The optimal conditions were rotation rate 200 r/min, molar ratio of methanol to oil 2.2: l, reaction temperature 43℃, and the catalyst amount 14% (based on the weight of oil). After reacting for 18 h, 67.5% of the oil was converted to its corresponding methyl esters (the theoretical ester conversion was 73.3%). The lipase was washed by organic solvents after each reaction and was reused again. The esters conversion of tung oil was decreased by 6% after the lipase was reused for 120 h. The theoretical amount of methanol was added in two steps, 85% ester conversion was obtained after 36 h of reaction (theoretical ester conversion was 100%). The molar ratio of methanol to oil, the catalyst amount, the reaction temperature, and reaction time were all highly significant factors, and there was a relative significant interaction between every two factors.
文摘The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1.
基金financial and moral support from the National Centre for Physics Islamabad,Pakistan to carry out of this present research workDeanship of Scientific Research at King Saud University for it’s funding of this research through the Research Group Project no RGP-VPP-345
文摘The non-edible oils are believed to be one of the major feedstock for the production of biodiesel in future.In the present study,we investigated the production of Jatropha oil methyl esters(JOMEs) via alkali-catalyzed transesterification route.The biophysical characteristics of Jatropha oil were found within the optimal range in accordance with ASTM standards as a substitute diesel fuel.The chemical composition and production yield of as-synthesized biodiesel were confirmed by various analytical techniques such as FT-IR,1H NMR,13 C NMR and gas chromatography coupled with mass spectrometry.A high percentage conversion,~96.09%,of fatty acids into esters was achieved under optimized transesterification conditions with 6 :1 oil to methanol ratio and 0.9 wt% Na OH for 50 min at ~60°C.Moreover,twelve fatty acids methyl esters(FAME) were quantified in the GC/MS analysis and it was interesting to note that the mass fragmentation pattern of saturated,monounsaturated and diunsaturated FAME was comparable with the literature reported values.
基金Supported by the National Natural Science Foundation of China(21576053)the Natural Science Foundation of Fujian Province(2016J01689)the Young Teacher Education Research Foundation of Fujian Province(JAT160056)
文摘The transesterification of palm oil and methanol catalyzed by Br?nsted acidic ionic liquids was investigated. Four eco-friendly Br?nsted acidic ionic liquids were prepared and their structures were characterized by NMR, FT-IR and TG–DTG. The results demonstrated that [CyN_(1,1)PrSO_3H][p-TSA] was more efficient than the other ionic liquids and chosen as catalyst for further research. The influences of various reaction parameters on the conversion of palm oil to biodiesel were performed, and the orthogonal test was investigated to seek the optimum reaction conditions, which were illustrated as follows: methanol to oil mole ratio of 24:1, catalyst dosage of 3.0 wt% of oil, reaction temperature of 120 °C, reaction time of 150 min, and the biodiesel yield achieved 98.4%. In addition, kinetic study was established for the conversion process, with activation energy and preexponential factor of 122.93 k J·mol^(-1) and 1.83 × 10^(15), respectively. Meanwhile, seven-time recycling runs of ionic liquid were completed with ignorable loss of its catalyst activity. The refined biodiesel met the biodiesel standard EN 14214.
基金the Unicamp Scholarship Program,CAPES and the financial support provided by FAPESP(Sao Paulo Research Foundation,Process 2013/25850-7)Prof.Dr.Milton Mori for giving space to perform the simulations and the Microfabrication Laboratory(Proposal LMF-19844)
文摘The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influence on fluid mixing and oil conversion was investigated for a range of operating conditions: Reynolds number(Re = 0.1–100),Temperature(25–75 °C), ethanol/oil molar ratio(6-12), and catalyst concentration(0.75 wt%–1.25 wt%), using three microchannel configurations(Length = 35 mm; Width = 1500 μm; Height = 200 μm): T-shape – channel without obstructions; MCO – channel with 3 obstructions ensemble – equally disposed over longitudinal length;MWO – channel with 7 obstructions ensemble. The MCO micromixer was based on literature work, and the MWO is a totally new micromixer design. Experimental tests were conducted in similar conditions in microreactors using these micromixers(Length = 411 mm) made of polydimethylsiloxane. The MCO configuration presented the highest performance(mixing index of 0.80 at Re = 100), oil conversion of 81.13% at 75 °C, molar ratio of 9 and catalyst concentration of 1%. Experimental results showed high conversions for MCO and MWO configurations(99.99%) at 50 °C, molar ratio of 9 and catalyst concentration of 1%, with a residence time of 12 s.
基金This work was supported by National Natural Science Foundation of China (No.20636030 No.20176008)Natural Science Foundation of Tianjin(No.07 JCZDJC00100)
文摘The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol has been investigated. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), thermogravimetry analysis (TG), atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterization. The results show that, the formation of Pb4O(OC6H5)6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead, which is the cause of the catalyst deactivation. In addition, the composition of the leached lead is ascertained to be a mixture of Pb4O(OC6H5)6 and PbO with the weight percentage of 62.7% and 37.3%, respectively.
文摘Biodiesel is an alternative renewable fuel which is produced by using biomass resources. Its physicochemical properties are close to those of the petroleum diesel fuel. This study highlights biodiesel production from safflower seed oil. The main aim of this experimental work is to optimize the process parameters, namely the methanolto-oil molar ratio, catalyst concentration, reaction time and reaction temperature for biodiesel production. The Taguchi robust design approach was used with an L9 orthogonal array to analyze the influence of process factors on performance parameters. The results showed that the optimum yield of biodiesel was 93.8% with viscosity 5.60 c St, with a methanol-to-oil molar ratio of 4:1, catalyst concentration of 1.5 wt%, reaction time of 90 min and reaction temperature of 60 ℃. The catalyst concentration was found to be the most influencing parameter which contributed 51.1% and 50.8% of the total effect on the yield of biodiesel, Y;, and viscosity of biodiesel, Y;, respectively.
基金This work was supported by the National Natural Science Foundation of China(20276050)Foundation for University Key Teacher by the Ministry of Educationthe Department of Science and Technology of Yunnan Province for the project on Technology Collaboration and Development in China.
文摘Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1 ( 2.5 wt% Ti ) catalyst. TS-1 catalyst, as a heterogeneous catalyst, showed excellent selectivity of diphenyl oxalate and methylphenyl oxalate compared with other homogeneous catalysts. Lewis acid sites on TS-1 catalyst were the active sites for transesterification of dimethyl oxalate with phenol. The high selectivity was closely related to the weak acid sites over TS-1.
基金Project(0805167) supported by China Postdoctoral Science FoundationProjects(30700349, 30700348) supported by the Scientific Research Foundation for Doctors in Henan Agricultural University, China+1 种基金Project(20735003) supported by the National Natural Science Foundation of ChinaProject(KJCX2YWH09) supported by Chinese Academy of Sciences
文摘It is hoped to develop a simple and low cost route for preparing the CaO with a novel morphology which can present high catalytic activity in catalyzing transesterification reaction for biodiesel. The porous CaO microsphere was synthesized by calcining spherical CaCO3 precursor which was prepared easily by mixing CaCl2 with Na2CO3. The as-prepared CaO microsphere was characterized by scanning electronic microscopy(SEM), powder X-ray diffractometry(XRD) and N2 adsorption experiment. The results reveal that the synthesized CaO is regular microsphere with many pores in its exterior and interior. The CaO microsphere is applied in catalyzing the transesterification reaction of soybean oil for biodiesel and presents excellent catalytic ability with a transesterification yield of 98.72%. This catalyst could have potential applications in other fields in view of its well-defined morphology, simply synthetic route and low cost.
基金Supported by the National Natural Science Foundation of China(Nos.20671011,20331010,90406002and90406024)the 111 Project(No.B07012)the Key Laboratory of Structural Chemistry Foundation(No.060017).
文摘A novel flower-like hydrated magnesium carbonate hydroxide, Mg5 (CO3 )4 (OH)2·4H2O, with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant. Reaction time has an important effect on the final morphology of the product. The micro-structure and morphology of Mg5 (CO3)4 (OH)2·4H2O were characterized by means of X-ray diffractometry (XRD), fieldemission scanning electron microscopy(FE-SEM). Brunauer-Emmett-Teller(BET) surface areas of the samples were also measured. The probable formation mechanism of flower-like micro-structure was discussed. It was found that Mg5 (CO3)4( OH)2·4H2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol.
基金supported by the National Natural Science Foundation of China(NSFC 21706163)the Foundation from Liaoning Province Department of Education(LQGD2017020)
文摘Four ionic liquids [BMIM]OH, [BMIM]IM, [BMIM]Br, and [BMIM]PF6 were synthesized and characterized by infrared spectroscopy. Then the effects of ionic liquids(ILs), cocatalysts, and reaction temperature on the catalytic performance for transesterification of ethylene carbonate and methanol were investigated with orthogonal experiments. The influence of cations and anions of ILs on catalytic activity was revealed by the density functional theory(DFT). The reaction mechanism was proposed based on the experimental results and DFT. The results demonstrated that the optimal catalyst was [Bmim]PF6/CaO, which exhibited the advantages of high activity, excellent stability, and easy recycling. Under the optimized conditions covering a catalytic temperature of 130 °C, an ionic liquid/cocatalyst mass ratio of 5:1, and a catalyst dosage of 4.0%, the conversion rate could reach 65.23% with a dimethyl carbonate selectivity of 98.95%. No significant loss of catalyst activity was detected after 7 recycle times.
文摘The synthesis of acyclovir and L-ascorbic acid with divinyladipate was performed with alkaline protease from Bacillus subtilis and lipase from Lipozyme (immobilized from Mucor miehei) in different anhydrous organic solvents. Two corresponding derivatives were obtained.
基金supported by the Key Projects in the National Science & Technology Pillar Program during the Eleventh Five-Year Plan Period(2006BAE02B03)
文摘The transesterification of diphenyl carbonate (DPC) with 1,4-butyldiol (BD) was kinetically investigated in the presence of lithium acetate catalyst at 465 K.The reaction was followed by the measurement of the quantity of phenol which was distilled from the reactor.The experiments supported the assumption that the phenyl ester groups in DPC and phenyl hdroxybutyl carbonate (PHBH) had the same reactivity,and the transesterification obeyed first-order kinetics with respect to DPC and BD,and a rate equation was derived.The reaction rate was found to be first order with respect to the catalyst concentration as well.When those data were incorporated in the rate equation,excellent agreement between calculated values and the observed ones was recognized over a wide range.
基金This work was supported by the National Natural Science Foundation of China(No.20173050)Natural Science Foundation of Shandong Province(No.Z2002F01).
文摘The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features of these compounds were described, and the possible mechanism of the novel transesterification was suggested.
文摘This research investigates the effect of reaction variables that strongly affect the cost of biodiesel production from non-edible Spirulina-Platensis microalgae lipids, and use the acid-catalyzed in situ transesterification process. Experiments were designed to determine how variations in volume of reacting methanol, the concentration of an acid catalyst, time, temperature and stirring affected the biodiesel yield. The total lipid content of Spirulina-Platensis microalgae was obtained to be 0.1095g/g biomass. The weight of the by-product glycerol obtained was used to predict the percentage yield conversion of microalgae oil biodiesel. Best results (84.7%), a yield of fatty acid methyl ester (FAME), were obtained at 100% (wt./wt.oil) catalyst concentration, 80 ml methanol volumes, 8 h reaction time and 65℃ reaction temperature with continuous stirring at 650 rpm. Properties of the produced biodiesel were measured according to EN 14214 standards.
文摘For transesterification of Jatropha oil into biodiesel, ultrasound assisted transesterification seems to be promising in terms of reduction in process time and stages of operation. Effects of process variables such as the catalyst loading, the molar ratio of methanol to oil, reaction temperature and the reaction time were investigated on the conversion of Jatropha oil to biodiesel. The conversion was above 93% under the conditions of 50?C, methanol to oil molar ratio of 9:1, reaction time 30 min and catalyst amount (catalyst/oil) of 1% wt%. A kinetic study of transesterification of Jatropha oil based on ultrasound assisted synthesis is presented in this paper. Rate equation obtained is also presented.