Production of mixed methyl/ethyl esters from waste fish oil through transesterification with mixed methanol/ethanol system

Biodiesel (mixed fatty acid methyl/ethyl esters) was prepared from waste fish oil through base-catalyzed transesterification with mixed methanol/ethanol system. Effect of methanol/ethanol (% v/v), type and concentration of the catalyst, mixed alcohols to oil molar ratio, the reaction temperature, and the reaction time on the biodiesel yield was optimized. Maximum biodiesel yield (97.30?wt%) was produced by implementing 1:1 methanol/ethanol (v/v), 1.0?wt% KOH, 6:1 mixed alcohols to oil molar ratio, 40°C reaction temperature, and 30?min of reaction time. Conversion of the waste fish oil to mixed methyl/ethyl esters was confirmed by ¹H NMR spectroscopy. Fuel properties of the resulting biodiesel in addition to its blends with petrodiesel were in good agreement with specifications of ASTM D6751 and ASTM D7467, respectively. Therefore, it was concluded that using mixed alcohol system for biodiesel production could reduce the production cost through reducing conditions required for maximum conversion.     

Biodiesel from activated sludge through in situ transesterification

BACKGROUND: The microbial biomass present in activated sludge contains lipidic compounds that can be used as biodiesel feedstock. In this study, the production of biodiesel from activated sludge from Tuscaloosa, AL was optimized based on the yield of fatty acid methyl esters (FAMEs). In situ transesterification was used with sulfuric acid as catalyst. A general factorial design of 4 × 6 × 5 for temperature, methanol to sludge ratio and catalyst concentration, respectively, was considered for optimization. RESULTS: Biodiesel yield can be adequately described by the quadratic response surface model with R² of 0.843 and statistically insignificant lack of fit (p = 0.152). Numerical optimization showed that an optimum biodiesel yield of 4.88% can be obtained at 55 °C, 25 methanol to sludge ratio and 4% volume sulfuric acid. The optimum experimental biodiesel yield was indeed obtained at that condition but with a value of 4.79 ± 0.02%. The highest error was 2.30% which indicates good agreement between the model and the experimental data. CONCLUSIONS: Acid‐catalyzed polymerization of unsaturated fatty acids or their esters at temperature above 60 °C significantly decreased biodiesel yield. The fatty acid profile of the biodiesel produced indicates that activated sludge may be used as biodiesel feedstock. Copyright © 2009 Society of Chemical Industry     

SOLID BASE CATALYZED TRANSESTERIFICATION OF CANOLA OIL

Catalytic activities of synthesized solid base catalysts (alumina loaded with solution of different potassium compounds such as KI, KF, K₂CO₃, and KNO₃ with the loading amount of 35 wt.%) were tested for the transesterification reaction of canola oil with methanol and ethanol in a batch reactor in a temperature range of 25–60°C and different feed ratios of methanol/oil between 6:1 and 18:1. Synthesized KF/Al₂O₃ solid base catalyst showed the highest activity in the transesterification of canola oil with methanol and gave much stabler methyl ester content during the reaction with the highest yield of 99.6% at the end of the eight-hour reaction time at 60°C, with a methanol/oil ratio of 15:1 and a catalyst amount of 3 wt.%. Formation of K₂O phase and the formation of the surface Al-O-K groups by salt-support interactions were observed during the synthesis of the catalysts. Methanol was found to be much more reactive than ethanol in the transesterification reaction.     

Molecular transport of organic esters and ketones into fluoropolymer membranes

The effect of different fluorine contents of DuPont VITON fluoropolymers and their transport characteristics in the presence of phenyl acetate, diethyl oxalate, diethyl malonate, diethyl succinate, acetone, methyl ethyl ketone and methyl iso-butyl ketone has been investigated over the temperature interval of 25?60°C. The average values of diffusion coefficients are obtained from the Fickian relation and the molecular transport is found to follow an anomalous behavior. Kinetic rate constants and pentration velocities are also calculated. The experimental results and the calculated quantities are studied in terms of polymer-solvent interactions.     

Transesterification Kinetics of Soybean Oil for Production of Biodiesel in Supercritical Methanol

A kinetic study on soybean oil transesterification without a catalyst in subcritical and supercritical methanol was made at pressures between 8.7 and 36 MPa. It was found that the conversion of soybean oil into the corresponding methyl esters was enhanced considerably in the supercritical methanol. The apparent activation energies of the transesterification are different with the subcritical and the supercritical states of methanol, which are 11.2 and 56.0 kJ/mol (molar ratio of methanol to oil: 42, pressure: 28 MPa), respectively. The reaction pressure considerably influenced the yield of fatty acid methyl esters (FAME) in the pressure range from ambient pressure up to 25 MPa (280 °C, 42:1). The reaction activation volume of transesterification in supercritical methanol is approximately −206 cm³/mol. The PΔV ^≠ term accounts for nearly 10% of the apparent activation energy, and can not be ignored (280 °C, 42:1).     

Synthesis of economically viable biodiesel from waste frying oils (WFO)

In present communication, waste frying oil (WFO) has been used as a feedstock for biodiesel synthesis. WFO, procured from a local Indian restaurant possessed an acid value of 0.84 mg KOH/g, which is low enough for single step transesterification reaction. Biodiesel (fatty acid methyl esters) was washed after transesterification reaction and the yield got lowered substantially (from 96% to 86.36%) after water washing owing to loss of esters. 30:100 vol% (methanol to oil), 0.6 wt% NaOCH₃, 60°C temperature and 600 rpm agitation in 1 h reaction time was found to be optimum for transesterification reaction. ¹H NMR spectrum showed a high conversion (95.19%) of fatty acids in WFO to biodiesel in 2 h reaction time. Almost complete conversion (99.68%) was attained in 2 h reaction time. © 2011 Canadian Society for Chemical Engineering     

The Optimization of the Production of Methyl Esters from Corn Oil Using Barium Hydroxide as a Heterogeneous Catalyst

In recent years, vegetable oils, as renewable raw materials, became a promising feedstock for chemicals and biodiesel production. The main products derived from oils are esters of fatty acids, especially methyl esters, obtained by their transesterification with methanol, in presence of acid or alkaline catalysts. The use of such catalysts implies the need for washing operations, which leads to environmental pollution. In the present paper, the response surface methodology based on a central composite design, has been developed to optimize the process of transesterification of corn oil. Ba(OH)₂ in presence of diethyl ether was used as catalyst. A quadratic polynomial equation was obtained. It correlates the reaction parameters [methanol/oil molar ratio (x _r), reaction time (x _t) and catalyst concentration (x _c)] with methyl esters yield. Analysis of variance analysis showed that only methanol/oil molar ratio and catalyst concentration have had the most significant influences on the conversion. The maximum methyl esters yield was obtained using the following optimum parameters: methanol/corn oil ratio of 11.32, reaction time of 118 min and catalyst concentration of 3.6 wt%.     

Thermal Decomposition Performance of Unsymmetrical Dimethylhydrazine (UDMH) Oxalate

The thermal decomposition behavior of unsymmetrical dimethylhydrazine (UDMH) oxalate was studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TG/DTG), and thermogravimetric analysis combined with infrared spectroscopy (TG‐IR). The endothermic decomposition of UDMH oxalate occurred at temperatures between 180.4 °C and 217.6 °C, the maximum decomposition temperature is 199.2 °C. The kinetic parameters of the decomposition reaction were calculated based on the Kissinger equation. The TG‐IR spectra indicated that the thermal main decomposition products of UDMH oxalate are CO₂,H₂O and NH₃.     

Ni-Na/Zr02-Mn02-Zn0催化合成甲基异丙基酮和二乙基酮（英文）

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.     

CO气相偶联合成草酸二乙酯反应热力学分析

采用Joback基团贡献法推导了亚硝酸乙酯的摩尔定压热容与温度的关系式,并估算了亚硝酸乙酯和碳酸二乙酯的标准摩尔生成吉布斯自由能.综合物性手册中各化合物的热力学函数,计算了CO偶联合成草酸二乙酯反应中主反应和副反应的反应热、反应吉布斯自由能和平衡常数,并对此进行了分析,发现较低的反应温度有利于草酸二乙酯的生成,且主反应...     

草酸二乙酯的生产工艺研究

研究了反应精馏合成草酸二乙酯的新工艺。在反应精馏塔内考察了挟带剂种类、塔釜温度、进料位置、回流进料比、原料醇酸物质的量比对酯化反应的影响,得到了优化的工艺条件,酯化率达90%。     

<Emphasis Type="Italic">In situ</Emphasis> alkaline transesterification: An effective method for the production of fatty acid esters from vegetable oils

The production of simple alkyl FA esters by direct alkali-catalyzed in situ transesterification of the acylglycerols (AG) in soybeans was examined. Initial experiments demonstrated that the lipid in commercially produced soy flakes was readily transesterified during agitation at 60°C in sealed containers of alcoholic NaOH. Methyl, ethyl, and isopropyl alcohols readily participated in the reaction, suggesting that the phenomenon is a general one. Statistical experimental design methods and response surface regression analysis were used to optimize reaction conditions, using methanol as alcohol. At 60°C, the highest yields of methyl ester with minimal contamination by FFA and AG were predicted at a molar ratio of methanol/AG/NaOH of 226∶1∶1.6 with an approximately 8-h incubation. An increase in the amount of methanol, coupled with a reduced alkali concentration, also gave high ester yields with low FFA and AG contamination. The reaction also proceeded well at 23°C (room temperature), giving higher predicted ester yields than at 60°C. At room temperature, maximal esterification was predicted at a molar ratio of 543∶1∶2.0 for methanol/AG/NaOH, again in 8 h. Of the lipid in soy flakes, 95% was removed under such conditions. The amount of FAME recovered after in situ transesterification corresponded to 84% of this solubilized lipid. Given the 95% removal of lipid from the soy flakes and an 84% efficiency of conversion of this solubilized lipid to FAME, one calculates an overall transesterification efficiency of 80%. The FAME fraction contained only 0.72% (mass basis) FFA and no AG. Of the glycerol released by transesterification, 93% was located in the alcoholic ester phase and 75 was on the post-transesterification flakes.     

Iron Oxide Catalysts Supported on Porous Silica for the Production of Biodiesel from Crude Jatropha Oil

A heterogeneous catalyst, FeO _x /SiO₂, prepared by the pore-filling method, was found to be active in the transesterification of crude Jatropha oil with methanol. When the transesterification reaction was carried out with a reaction temperature of 220?°C, a catalyst amount of 15?wt%, a methanol/oil molar ratio of 218:1, and a reaction time of 3?h, the yield of fatty acid methyl esters (FAME) in the product exceeded 99.0?%, and met with EN standards for allowable contents of glycerine and mono-, di-, and tri-glycerides. The correlation between the FAME production activity and measured acidity of the FeO _x /SiO₂ catalysts showed that the transesterification reaction was promoted via the acidic function of these catalysts, which are less inhibited by coexisting free fatty acids in the feedstock triglycerides.     

Kinetic study of the base-catalyzed transesterification of monoglycerides from <Emphasis Type="Italic">pongamia</Emphasis> oil

The kinetics of the transeterification of vegetable oil is known to follow a three-step reaction mechanism. The third step involves the transesterification of MG. In this study, the transesterification of MG obtained from crude Pongamia oil was achieved with methanol in the presence of KOH as the catalyst. A MG/methanol ratio of 1∶10 was used at different temperatures (30, 45, 55, and 60°C). ¹H NMR was used to monitor the progress of transesterification. The study revealed that the kinetics of this reaction followed a reversible second-order model, with a good fit obtained for all temperatures except 30°C. This result is explained as arising out of the importance of transport effects at low temperatures. The forward rate constant increased with an increase in temperature, whereas the reverse rate constant showed a decreasing trend, suggesting that the proposed reverse reaction was not an elementary step.     

Lipase-catalyzed synthesis of triolein-based sunscreens in supercritical CO2

Novozym^® 435-catalyzed transesterification of ethyl 4-hydroxy-3-methoxy cinnamate (ethyl ferulate, EF) with triolein to form the ultraviolet (UV)-absorbing lipids monoferuloylmonooleoyl-glycerol (FMO) and feruloyl-dioleoyl-glycerol (FDO) has been conducted using supercritical CO₂ (SC?CO₂) batch reactions. The alcoholysis of 0.1 M EF with 0.1 M 1-octanol in SC?CO₂ to form octyl ferulate was used as a model reaction to optimize pressure and temperature conditions. Conditions ranging from 45 to 80°C and 10.3 to 34.5 MPa (1,500 to 5,000 psi) were tested with a maximal conversion of 53% of the EF being achieved at 13.8 MPa (2,000 psi) and 80°C after 24 h. These optimized conditions applied to the transesterification of EF with triolein effected a combined FMO and FDO yield of 69%. Triolein exhibits higher solubilities in SC?CO₂ at higher pressures; therefore, the transesterification was performed at 80°C over a range of pressures from 13.8 to 34.5 MPa (2,000 to 5,000 psi). Results showed that a maximal yield of 74% of FMO and FDO was reached at 80°C and 24.1 MPa (3,500 psi) after 48 h. Compared to the FMO and FDO synthesis conducted neat or in toluene, the synthesis of the UV-absorbing lipids in SC?CO₂ affords higher yields within a shorter amount of time. Therefore, the transesterification of EF with triolein in a SC?CO₂ batch reaction is a viable route to UV-absorbing lipids that could be used as active ingredients in sunscreen formulations.     

合成草酸二乙酯新工艺的研究

研究了反应精馏合成草酸二乙酯新工艺。开发了一种适用于草酸乙酯化的反应精馏塔,确定了适宜的工艺条件：D2为进料位置,n（C2H5OH）∶n（C2H4O4）=10∶1、V（回流量）∶V（进料量）=3∶1、进料速度为0.8 mL/min,草酸二乙酯的酯化率可达到98%左右,并且采用反应精馏合成草酸二乙酯的时空收率为间歇釜式反应器合成草酸二乙酯时空收率的3.5~4倍。     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Study of the acid pretreatment and biodiesel production from olive pomace oil

The objective of this work was to study the two‐step acid base homogenous catalyzed transesterification of olive pomace oil, with the ultimate purpose of producing biodiesel under mild reaction conditions by optimizing the process. Optimization of the experimental procedure was conducted by a factorial design of 2³ under the acidic pretreatment step and during the basic transesterification. The optimal production of methyl esters (97.8%) was achieved for the experimental conditions H₂SO₄ = 20 wt%/CH₃OH = 35:1/T = 40^°C and KOH = 0.6+ fatty acid value /CH₃OH = 9:1/ T = 60^°C, in the acidic and basic stage of the process, respectively. Finally, to properly assess the quality of the biofuel produced, it was tested for all the European Standard properties.     

Reaction Kinetics and Mechanisms for Hydrolysis and Transesterification of Triglycerides on Tungstated Zirconia

Hydrolysis and transesterification are two reactions which can occur during the synthesis of biodiesel. An Investigation of the mechanistic pathways in hydrolysis and transesterification were carried out at a relatively high temperature (100–130 °C) and moderate pressures (120–180 psi) with tricaprylin and water for hydrolysis or methanol for transesterification using a tungstated zirconia catalyst in a batch reactor. It was found that upon increasing the concentration of TCp, the reaction rates for both hydrolysis and transesterification increased at all conditions. In contrast, water inhibited the reaction rate of hydrolysis by poisoning the active sites. For transesterification, the apparent reaction order of methanol evolved from positive to negative as the concentration of methanol relative to TCp increased. Using a reaction model discrimination procedure, it was found that hydrolysis on WZ could be successfully described by an Eley–Rideal single site mechanism with adsorbed TCp reacting with bulk phase water. The mechanistic pathway for transesterification also seems to follow a similar mechanism, identical to the one previously proposed for transesterification on a solid acid catalyst (SiO₂-supported Nafion-SAC-13) at lower temperature (60 °C).     

Preparation and characterization of ferrous oxalate cement—A novel acid-base cement

Ferrous oxalate cement (FOC), a new type of acid-base cement, is prepared at room temperature through reactions between iron-rich copper slag (CS) and oxalic acid (OA). In this work, the influences of precursor proportions, including the copper slag-to-oxalic acid mass ratio (CS/OA), borax-to-cement mass ratio (B/C), and water-to-cement mass ratio (W/C), on the setting behavior and compressive strength of FOC paste are investigated. Furthermore, the evolutions of pH and ions concentrations are traced to understand the reaction mechanism of FOC. The results show that the compressive strength decreases with an increase in W/C; when W/C is fixed, with an increase in CS/OA, the compressive strength first increases and then decreases, giving an optimal value. The compressive strengths of specimens at 3, 7, and 28 days can reach 33, 41, and 55 MPa, respectively, under the optimal conditions (CS/OA = 3.6, B/C = 0.03, and W/C = 0.18). The setting time is also a function of W/C and CS/OA, and can be extended by adding borax. Iron oxalate hydrate (FeC₂O₄·2H₂O) has been identified as the exclusive hydration product of FOC due to the chemical reaction between Fe₂SiO₄ or Fe₃O₄ contained in CS and OA solution. At the initial stage of reaction, OA is dissolved to release protons, HC₂O₄⁻ and C₂O₄²⁻, which facilitate the dissolution of Fe₂SiO₄ and Fe₃O₄ and the release of Fe²⁺ in the aqueous phase. Then the Fe²⁺ ions combine with HC₂O₄⁻ and C₂O₄²⁻ to precipitate FeC₂O₄·2H₂O, acting as the cementitious phase to bond the unreacted CS particles.