Biodiesel from Citrullus colocynthis oil: sulfonic-ionic liquid-catalyzed esterification of a two-step process.
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ABSTRACT: Biodiesel was prepared from Citrullus colocynthis oil (CCO) via a two-step process. The first esterification step was explored in two ionic liquids (ILs) with 1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHSO4) and 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate (MSIMHSO4). Both ILs appeared to be good candidates to replace hazardous acidic catalyst due to their exceptional properties. However, the two sulfonic chains existing in DSIMHSO4 were found to increase the acidity to the IL than the single sulfonic chain in MSIMHSO4. Based on the results, 3.6 wt% of DSIMHSO4, methanol/CCO molar ratio of 12 : 1, and 150 °C offered a final FFA conversion of 95.4% within 105 min. A 98.2% was produced via second KOH-catalyzed step in 1.0%, 6 : 1 molar ratio, 600 rpm, and 60 °C for 50 min. This new two-step catalyzed process could solve the corrosion and environmental problems associated with the current acidic catalysts.
Project description:Ionic liquids (ILs) are recyclable, non-volatile, and can dissolve cellulose, a natural polymer that is insoluble in versatile solvents. Therefore, ILs have been used to modify cellulose. However, 1-ethyl-3-methylimidazolium acetate (EmimOAc), a commercially available IL often used to dissolve and modify cellulose to prepare cellulose-based materials, causes the undesired introduction of an acetyl group derived from the acetate anion of EmimOAc onto the hydroxy group of cellulose during esterification. In this study, for cellulose esterification, we prepared aryloxy ILs as non-carboxylate-type and basic ILs, which can theoretically prevent the undesired introduction of an acyl group from the IL onto the hydroxy group of cellulose. The optimized 1-ethyl-3-methylimidazolium 2-pyridinolate (Emim2OPy) and mixed solvent system achieved rapid cellulose esterification (within 30 min) with an excellent degree of substitution (DS) value (up to >2.9) derived from the employed low-reactive vinyl esters and bio-based unsaturated aldehydes, without any undesired substituent introduction from side reactions.
Project description:Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70 °C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64 °C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis.
Project description:In this investigation, we report the synthesis of biodiesel using benzimidazolium-based brønsted acid ionic liquid (BBAIL) catalyst under the influence of ultrasonication. The prepared BBAIL catalyst was characterized by Fourier transform infrared and NMR spectroscopy techniques, and its acidity was determined by the Hammett method with 4-nitroaniline as the indicator. Ultrasonicator horn (22 kHz, 500 W) was used in this work with an on-off cycle of 50-20 s at 70% amplitude. The highest biodiesel yield of 96% was achieved by ultrasonication when 1:10 molar ratio of castor oil to methyl alcohol was used at 50 °C temperature with 9 mol % of the catalyst in just 90 min, which is about 10 times lesser than the process without ultrasonication. At similar conditions, 96% biodiesel yield was obtained in 14 h without ultrasonication. In summary, ultrasonication proved to be an efficient way to improve biodiesel synthesis in less time and BBAIL showed excellent activity toward the conversion of glycerides to synthesize biodiesel. Other important highlights are easy separation of the catalyst and recyclability up to three cycles with small decrease in its activity.
Project description:A morpholine alkaline basic ionic liquid (IL) 1-butyl-3-methyl morpholine hydroxide ([Hnmm]OH) was synthesized and characterized by ¹H NMR and FT-IR. [Hnmm]OH is highly active in catalyzing the synthesis of biodiesel from the reaction of methanol with soybean oil. The influence of the reaction conditions, including the [Hnmm]OH catalyst amount, the molar ratio of methanol to soybean oil, reaction temperature and time, was investigated. Moreover, the pH and thermal stability of the catalyst was studied. The catalytic activity was affected by its alkalinity. The optimum reaction conditions were found as [Hnmm]OH amount of 4% (mass fraction), the methanol to soybean oil molar ratio of 8, temperature 70 °C and reaction time 1.5 h, the yield of Biodiesel reached 97.0%, and exhibits high stability upon recycling, the yield of Biodiesel is still more than 90% even after being reused for five times. A great advantage of using ILs is that it is very easy to separate the final products. After the reaction, a biphasic system was obtained. The top phase contains biodiesel and a little bit of methanol. Pure biodiesel can be isolated by vacuum evacuating the methanol. The bottom phase contains methanol, glycerol and ILs. Pure glycerol can be obtained simply by distillation. After distillation, pure ILs was obtained, which can be used directly for another reaction. The as prepared biodiesel shows very appealing properties.
Project description:We describe the enzymatic synthesis of biodiesel from waste cooking oil (WCO) in a two-step production process: hydrolysis of WCO, followed by acid-catalyzed esterification of free fatty acids (FFAs). Among the three commercial enzymes evaluated, the inexpensive lipase Lipex® 100L supported on Lewatit® VP OC 1600 produced the best overall biodiesel yield (96.3%). Finally, we assessed the combustion efficiency of the obtained biodiesel and its blends. All blends tested presented lower emissions of CO and HC compared to diesel. The NOx emissions were higher due to biodiesel's high volatility and viscosity. The cost of biodiesel production was calculated using the process described.
Project description:Alternatives to petroleum-based plastics are of great significance not only from the point of view of their scientific and practical impact but to reduce the environmental footprint. Inspired by the composition and structure of wood's cell walls, we used phenolic acids to endow cellulosic fibers with new properties. The fiber dissolution and homogeneous modification were performed with a recyclable ionic liquid (IL) (tetrabutylammonium acetate ([N4444][OAc]):dimethyl sulfoxide) to attain different levels of reaction activity for three phenolic acids ( p-hydroxybenzoic acid, vanillic acid, and syringic acid). The successful autocatalytic Fischer esterification reaction was thoroughly investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, elemental analysis, and nuclear magnetic resonance spectroscopy (13C CP-MAS, diffusion-edited 1H NMR and multiplicity-edited heteronuclear single quantum coherence). Control of the properties of cellulose in the dispersed state, welding, and IL plasticization were achieved during casting and recrystallization to the cellulose II crystalline allomorph. Films of cellulose carrying grafted acids were characterized with respect to properties relevant to packaging materials. Most notably, despite the low degree of esterification (DS < 0.25), the films displayed a remarkable strength (3.5 GPa), flexibility (strains up to 35%), optical transparency (>90%), and water resistance (WCA ∼ 90°). Moreover, the measured water vapor barrier was found to be similar to that of poly(lactic acid) composite films. Overall, the results contribute to the development of the next-generation green, renewable, and biodegradable films for packaging applications.
Project description:BackgroundIn this study, a two-step processing method (hydrothermal liquefaction followed by catalytic upgrading) was used to produce upgraded bio-oil. A comprehensive screening analysis of algal species, including four microalgae and four macroalgae, was conducted to bridge the gap between previous accounts of microalgae and macroalgae hydrothermal liquefaction and the upgrading process of the resulting crude bio-oils.ResultsHydrothermal liquefaction using eight algal biomasses was performed at 350 °C for 1 h. The microalgae always produced a higher crude bio-oil yield than the macroalgae due to their high lipid content, among which Schizochytrium limacinum provided the maximum crude bio-oil yield of 54.42 wt%. For microalgae, higher amounts of N in the biomass resulted in higher amounts of N in the crude bio-oil; however, contrary results were observed for the macroalgae. The crude bio-oils generated from both the microalgae and macroalgae were characterized as having a high viscosity, total acid number, and heteroatom content, and they were influenced by the biochemical compositions of the feedstocks. Next, all eight-crude bio-oils were treated at 400 °C for 2 h with 10 wt% Ru/C using tetralin as the hydrogen donor. The hydrogen source was provided after tetralin was transformed to naphthalene. All the upgraded bio-oils had higher energy densities and significantly lower N, O, and S contents and viscosities than their corresponding crude bio-oils. However, the H/C molar ratio of the upgraded bio-oils decreased due to the absence of external hydrogen relative to the crude bio-oils. The S content of the upgraded bio-oil produced from upgrading the Schizochytrium limacinum crude bio-oil was even close to the 50 ppm requirement of China IV diesel.ConclusionsMicroalgae are better feedstocks than macroalgae for liquid fuel production. Biochemical components have a significant impact on the yield and composition of crude bio-oil. Tetralin does not perform as well as external hydrogen for controlling coke formation. The S content of the upgraded bio-oil can be reduced to 76 ppm for the crude bio-oil produced from Schizochytrium limacinum. Upgraded bio-oils have similar properties to those of naphtha and jet fuel.
Project description:Biodiesel synthesis from non-edible vegetable oil via catalytic transesterification is one of the effective ways to replace petroleum-based fuels in the area of renewable energy development and is beneficial to environmental security. Therefore, this research investigates the optimization of process parameters (temperature, methanol to oil ratio, and NaOH catalyst dose) for the conversion of biodiesel from non-edible desert date (Balanites Aegyptiaca) seed kernel oil using the Box-Behnken experimental design of response surface methodology statistical analysis. Accordingly, the optimum values of reaction conditions, namely, a temperature of 60.5 °C, methanol to oil ratio of 6.7:1, and catalyst dose of 0.79 %wt, yielded 93.16% biodiesel. Fourier transform infrared spectroscopy analysis confirmed the cracking of a single glycerol backbone from the triglycerides and the substitution by methoxyl in the presence of a NaOH catalyst. The physicochemical properties of the biodiesel were investigated and compared with standards in terms of its density, viscosity, higher heating value, acid value, saponification value, cetane number, cloud point, pour point, and flash point, and the values are within the recommended standard limits of American Standard for Testing Material (ASTM D6751) and European Committee for Standardization (EN14214). Thus, the results revealed that homogeneous base catalysis of non-edible oil under optimum reaction conditions provides high yield of biodiesel.
Project description:The optimum conditions to produce palm fatty acid distillate (PFAD)-derived-methyl esters via esterification have been demonstrated with the aid of the response surface methodology (RSM) with central composite rotatable design in the presence of heterogeneous acid catalyst. The effect of four reaction variables, reaction time (30-110 min), reaction temperature (30-70°C), catalyst concentration (1-3 wt.%) and methanol : PFAD molar ratio (3 : 1-11 : 1), were investigated. The reaction time had the most influence on the yield response, while the interaction between the reaction time and the catalyst concentration, with an F-value of 95.61, contributed the most to the esterification reaction. The model had an R 2-value of 0.9855, suggesting a fit model, which gave a maximum yield of 95%. The fuel properties of produced PFAD methyl ester were appraised based on the acid value, iodine value, cloud and pour points, flash point, kinematic viscosity, density, ash and water contents and were compared with biodiesel EN 14214 and ASTM D-6751 standard limits. The PFAD methyl ester was further blended with petro-diesel from B0, B3, B5, B10, B20 and B100, on a volumetric basis. The blends were characterized by TGA, DTG and FTIR. With an acid value of 0.42 (mg KOH g-1), iodine value of 63 (g.I2/100 g), kinematic viscosity of 4.31 (mm2 s-1), the PFAD methyl ester has shown good fuel potential, as all of its fuel properties were within the permissible international standards for biodiesel.
Project description:BackgroundEnzymatic biodiesel is becoming an increasingly popular topic in bioenergy literature because of its potential to overcome the problems posed by chemical processes. However, the high cost of the enzymatic process still remains the main drawback for its industrial application, mostly because of the high price of refined oils. Unfortunately, low cost substrates, such as crude soybean oil, often release a product that hardly accomplishes the final required biodiesel specifications and need an additional pretreatment for gums removal. In order to reduce costs and to make the enzymatic process more efficient, we developed an innovative system for enzymatic biodiesel production involving a combination of a lipase and two phospholipases. This allows performing the enzymatic degumming and transesterification in a single step, using crude soybean oil as feedstock, and converting part of the phospholipids into biodiesel. Since the two processes have never been studied together, an accurate analysis of the different reaction components and conditions was carried out.ResultsCrude soybean oil, used as low cost feedstock, is characterized by a high content of phospholipids (900 ppm of phosphorus). However, after the combined activity of different phospholipases and liquid lipase Callera Trans L, a complete transformation into fatty acid methyl esters (FAMEs >95%) and a good reduction of phosphorus (P <5 ppm) was achieved. The combination of enzymes allowed avoidance of the acid treatment required for gums removal, the consequent caustic neutralization, and the high temperature commonly used in degumming systems, making the overall process more eco-friendly and with higher yield. Once the conditions were established, the process was also tested with different vegetable oils with variable phosphorus contents.ConclusionsUse of liquid lipase Callera Trans L in biodiesel production can provide numerous and sustainable benefits. Besides reducing the costs derived from enzyme immobilization, the lipase can be used in combination with other enzymes such as phospholipases for gums removal, thus allowing the use of much cheaper, non-refined oils. The possibility to perform degumming and transesterification in a single tank involves a great efficiency increase in the new era of enzymatic biodiesel production at industrial scale.