Soybean Transesterification Research Articles

Preparation of cancrinite-type zeolite from diatomaceous earth as transesterification catalysts for biodiesel production

A new type of solid catalyst prepared from hydrothermal reaction of natural diatomaceous earth in NaOH solution was studied for biodiesel production through the transesterification of soybean and palm oil in excess methanol. Explicitly, the natural diatomite was transformed into efficacious catalysts, sequentially, by dispersion and activation in NaOH solutions for 30 min at 30 °C, followed by hydrothermal treatments at 180 °C or 220 °C for 12 h, and finally by calcination at 500 °C for 6 h. Coincidently, the physicochemical characteristics of these as-prepared catalysts were shown to bear a good resemblance with those of zeolite CAN. Under suitable conditions, the conversion efficiencies of soybean and palm oils to biodiesel in presence of these zeolite CAN catalysts at 63 °C and 70 °C could be obtained as high as 98.0% and 98.4%, respectively. Furthermore, the activation energies of the transesterification reactions of soybean and palm oils in excess methanol were found as 64.1 kJ/mol and 122.5 kJ/mol, respectively.

SIMULATION AND OPTIMIZATION OF CONTINUOUS BIODIESEL PRODUCTION FROM SOYBEAN OIL

It is known that oil and its derivatives were the main energetics of the last century, although the fact that these inputs are finite and generate several pollutant harmful to human health and the environment. Economic and environmental aspects have contributed to the gradual disuse of fossil fuels and to the growth of research on renewable and clean energy, such as biodiesel, that has been gaining representativeness in the national and world market. Brazilian biodiesel production has been led by soybean oil for many years, then, aiming to make the simulation of the biodiesel plant closer to the brazilian reality (based on biodiesel process described by Zhang et al., 2003) the raw material (triolein) was changed to (trilinolein) through the use of the predictive methods of Constantinou e Gani (1994) and (1995) to estimate base and critical properties. Besides, a kinetic equation based on the experimental data of Noureddini and Zhu (1997) was proposed to represent the rate of soybean transesterification in function of temperature. Finally, optimization studies were made with the objective of maximizing biodiesel production; minimize the consumption of energy and inputs; outline great scenarios from the environmental perspective. The optimization results indicated that the temperature of the conversion reactor has a great influence on the biodiesel production due to the linear relationship. In addition, the change in the flow of water inserted in the liquid-liquid extractor is insignificant in view of the influence of the reactor temperature.It is known that oil and its derivatives were the main energetics of the last century, although the fact that these inputs are finite and generate several pollutant harmful to human health and the environment. Economic and environmental aspects have contributed to the gradual disuse of fossil fuels and to the growth of research on renewable and clean energy, such as biodiesel, that has been gaining representativeness in the national and world market. Brazilian biodiesel production has been led by soybean oil for many years, then, aiming to make the simulation of the biodiesel plant closer to the brazilian reality (based on biodiesel process described by Zhang et al., 2003) the raw material (triolein) was changed to (trilinolein) through the use of the predictive methods of Constantinou e Gani (1994) and (1995) to estimate base and critical properties. Besides, a kinetic equation based on the experimental data of Noureddini and Zhu (1997) was proposed to represent the rate of soybean transesterification in function of temperature. Finally, optimization studies were made with the objective of maximizing biodiesel production; minimize the consumption of energy and inputs; outline great scenarios from the environmental perspective. The optimization results indicated that the temperature of the conversion reactor has a great influence on the biodiesel production due to the linear relationship. In addition, the change in the flow of water inserted in the liquid-liquid extractor is insignificant in view of the influence of the reactor temperature.

Transesterification of soybean and castor oil with methanol and butanol using heterogeneous basic catalysts to obtain biodiesel

This paper focuses on the preparation and characterization of CaO, MgO and ZnO, both bulk and supported on γ-Al2O3 and their catalytic activity in the transesterification of soybean oil and castor oil with methanol and butanol in order to produce biodiesel. XRD, SEM, CO2-adsorption followed by TGA and N2 adsorption have been employed to characterize the prepared catalysts. In supported catalysts, the presence of γ-Al2O3 improves alcohol dissociation on the superficial basic sites. The first step of the reaction mechanism is then favored (hydrogen abstraction). In the transesterification of castor oil with butanol, MgO/γ -Al2O3 and ZnO/γ-Al2O3 catalysts showed high yields to FABE (Fatty Acid Butyl Ester) (97% and 85%, respectively). These last catalysts constitute an efficient alternative for obtaining second-generation biodiesel, taking into account that castor oil is a nonedible source and butanol is an alcohol that can be obtained from biomass.

Enhancement of the valorization of renewable glycerol: The effects of the surfactant-enzyme interaction on the biocatalytic synthesis of glycerol carbonate

The effect of the addition of a surfactant during the bio-conversion of a renewable glycerol into glycerol carbonate (GlyC) has been investigated. Lipase enzyme immobilized on magnetic particles assisted the GlyC synthesis via the carbonylation of glycerol originating from different oils with dimethyl carbonate (DMC). Glycerol from food production residues was compared with glycerol produced from the transesterification of soybean, rape, olive, palm, sunflower, and corn oils. Tween 20, Tween 80, Triton X or CTAB was added as surfactant in the biocatalytic system with the scope to enhance the biocatalyst performance via a direct surfactant-lipase interaction. Optimum conditions of the system were set up testing different types and concentrations of surfactant. Indeed, the biocatalyst exhibited a higher catalytic activity in the presence of the surfactant. Thus, TON increased from 13.0×105 to 22.6×105 using only 0.1% (w/w) CTAB. Beside these, the effect of the lipase-surfactant interaction was investigated in the context of biocatalyst preparation and storage conditions.

Performance of CaO from different sources as a catalyst precursor in soybean oil transesterification: Kinetics and leaching evaluation

Calcium oxide (CaO) has been studied as one of the most efficient heterogeneous catalysts for methyl esters production, but there are few studies about the effects of CaO morphology on calcium leaching and catalyst activity. In the present work, soybean transesterification was performed using CaO from different sources (commercial, synthesized from chicken eggshell and produced by a carbothermal route) to develop a comparative study. The 1H NMR results showed that the soybean oil transesterification catalyzed with CaO, derived from all sources, yielded greater than 93% (m/m) methyl esters, 4h reflux, a molar methanol: oil ratio of 12:1 and 3% catalyst. The amount of leached calcium was 219ppm for the methyl esters synthesized with CaO derived from commercial sources, 194ppm for CaO from eggshell and 93ppm for CaO s from a carbothermal route. As consequence of higher Ca leaching content, CaO-com precursor presented higher rate constant. This can be explained by the prompt reaction of Ca leaching and glycerol, yielding calcium diglyceroxide, which is the main catalytic specimen. The study showed that the homogeneous contribution from the leached species can be considered negligible. The heterogeneous catalysis was confirmed for all different CaO sources studied.

Metal-cellulose catalytic systems for biodiesel preparation and reductive stabilization

Development of green processes is of the most important field of today’s research, with direct impacts on future generations, contributing to environmental and economic technologies. In this sense, the use of biomass is an attractive way in search of the green chemistry goals. This manuscript presents the modification of cellulose in order to complex tin, palladium and nickel cations, and the use of the obtained material as a catalyst for biodiesel preparation and partial hydrogenation. Reactions yields for soybean transesterification and hydrolysis and soybean fatty acids esterification using Sn (II) complexed with modified cellulose rendered yields up to 55%, 93% and 95%, respectively. Partially hydrogenation leading to monounsaturated chains were achieved using palladium and nickel derivatives under mild conditions (10bar; 80°C). These highly efficient catalytic systems could be recovered at the end of the process and reused without any loss of catalytic activity.

Biodiesel Production with Nanotubular Sodium Titanate Doped with Potassium as a Catalyst

ABSTRACTIn the present work, sodium titanate nanotubes doped with potassium were synthesized by the Kasuga method and tested as catalysts for biodiesel production. Potassium was added to the nanotubes in order to increase their basicity and, consequently, improve their performance in the transesterification of soybean oil with methanol. In the synthesis, the NaOH:KOH molar ratio was changed from 9:1 to 7:3 in order to increase potassium loadings in the obtained nanotubular solids. Synthesized catalysts were characterized by N2 physisorption, powder XRD, scanning electron microscopy (SEM-EDX), transmission electron microscopy (TEM), FT-IR, FT-Raman and CO2 temperature-programmed desorption (CO2-TPD). Obtained results showed that sodium trititanate nanotubes containing 1.5 wt. % of potassium were obtained when 10 M alkali solution with NaOH:KOH molar ratio of 9:1 was used. In this case, the proportion of sodium and potassium in the synthesized material was similar to that used in the synthesis. An increase in the proportion of KOH to 20 and 30 molar % in the NaOH-KOH solutions used in the synthesis allowed obtaining titanate nanotubes with larger potassium loadings (3.2 and 3.3 wt. %, respectively). As it was expected, potassium addition to the sodium titanate nanotubes resulted in an increase in the amount of medium and strong basic sites. Potassium-containing nanotubes showed higher catalytic activity in the transesterification reaction than the pure sodium counterpart used as a reference. The best results were obtained with the samples containing 3.2-3.3 wt. % of potassium where a biodiesel yield of about 94-96 % was obtained at 80 °C and 1 h reaction time.

Influence of oil quality on biodiesel purification by ultrafiltration

In the present study, biodiesel was produced by ethylic transesterification of soybean and canola oils using sodium hydroxide as a catalyst. It was evaluated the influence of oil quality on the biodiesel and glycerol separation by ultrafiltration. The experiments were carried out with tubular a-Al2O3/TiO2 membranes with average pore diameter of 0.05µm and 20kDa, varying the transmembrane pressure and the concentration of the feed mixture. The comparison among the use of degummed soybean oil, refined soybean oil, crude canola oil, and refined canola oil, demonstrated that free fatty acid presented in the oils influence the formation of droplets containing glycerol. The separation was efficient when reaction mixture was produced from degummed soybean oil and crude canola oil, both with a higher acidity value. The highest free fatty acid content in the crude canola oil, not only favored the formation of a dispersed phase containing glycerol, which was retained by the membrane, but also resulted in the lowest flux decline rates. The ultrafiltration was efficient in removing glycerol, since the highest glycerol content in the permeate was 0.013wt%. This novel refining process of biodiesel showed the advantage of not requiring previous decantation to separate the two phases obtained after transesterification and the reduction in the amount of water used in the washing steps. The properties of the biodiesel produced, which were evaluated, meet the ANP biodiesel standards required for marketing.

Lipase-catalyzed biodiesel production and quality with Jatropha curcas oil: exploring its potential for Central America.

BackgroundExtensive native Jatropha curcas L. (Jatropha) crop areas have been planted in Central America marginal lands since 2008 as a non-edible prospective feedstock alternative to high-value, edible palm oil. Jatropha biodiesel is currently exclusively produced in the region at commercial scale utilizing alkaline catalysts. Recently, a free, soluble Thermomyces lanuginosus (TL) 1,3 specific lipase has shown promise as biocatalyst, reportedly yielding up to 96 % ASTM D6751 compliant biodiesel after 24 h transesterification of soybean, canola oils and other feedstocks. Biodiesel conversion rate and quality of enzymatically catalyzed transesterification of Jatropha oil was evaluated. Two lipases: free, soluble TL and immobilized Candida antarctica (CA) catalyzed methanolic transesterification of crude Jatropha and refined palm oil.ResultsJatropha yields were similar to palm biodiesel with NaOH as catalyst. After 24 h transesterification, Jatropha (81 %) and palm oil (86 %) biodiesel yields with TL as catalyst were significantly higher than CA (<70 %) but inferior to NaOH (>90 %). Enzymatic catalysts (TL and CA) produced Jatropha biodiesel with optimum flow properties but did not complied with ASTM D6751 stability parameters (free fatty acid content and oil stability index).ConclusionsBiodiesel production with filtered, degummed, low FFA Jatropha oil using a free liquid lipase (TL) as catalyst showed higher yielding potential than immobilized CA lipase as substitute of RBD palm oil with alkaline catalyst. However, Jatropha enzymatic biodiesel yield and stability were inferior to alkaline catalyzed biodiesel and not in compliance with international quality standards. Lower quality due to incomplete alcoholysis and esterification, potential added costs due to need of more than 24 h to achieve comparable biodiesel yields and extra post-transesterification refining reactions are among the remaining drawbacks for the environmentally friendlier enzymatic catalysis of crude Jatropha oil to become an economically viable alternative to chemical catalysis.

Biodiesel production from soybean and Jatropha oils by magnetic CaFe2O4–Ca2Fe2O5-based catalyst

Heterogeneous CaFe2O4–Ca2Fe2O5-based catalyst with weak magnetism was prepared by co-precipitation and calcination. It was characterized by various techniques including X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed desorption method. Its active components were identified as mainly Ca–Fe composite oxides such as CaFe2O4 for transesterification. The magnetism was further strengthened by reducing its component of Fe2O3 to Fe3O4–Fe under H2 atmosphere for better magnetic separation. Both catalysts were used for the catalytic transesterification of soybean and Jatropha oils to biodiesel. The highest biodiesel yields for soybean oil of 85.4% and 83.5% were obtained over the weak and strong magnetic catalysts, respectively under the optimized conditions (373 K, 30 min, 15/1 methanol/oil molar ratio and 4 wt% catalyst). The catalysts could be recycled three times. Biodiesel production from pretreated Jatropha oil was tested with the magnetic CaFe2O4–Ca2Fe2O5–Fe3O4–Fe catalyst, and 78.2% biodiesel yield was obtained. The magnetic CaFe2O4–Ca2Fe2O5-based catalyst shows a potential application for the green production of biodiesel.

Comparatives Study of Production Biodiesel from Soybean oil and Jatropha Curcas Seeds Oil

ABSTRACT This study involves transesterification of soybean and Jatropha oils with methanol, using sodium hydroxide as the catalyst to produced biodiesel as an alternative to petroleum diesel. This work investigates the effects of temperature and time on the production of biodiesel from the feed stocks employed. Also investigated are the effects of particle size and temperature on the production of oil from the Jatropha seed. The produced biodiesels from soybean and Jatropha oil were characterised to determine their suitability as a replacement for the petrol diesel. Results obtained shows that both temperature and time influence the production of biodiesel from the soybean and Jatropha oil. Analyses of the produced biodiesels also indicates that the properties of the biodiesels produced shows that the density, refractive index, moisture content, viscosity, flash point, cetane number, pour point and sulphur content of the biodiesel produced from soybean oil are 0.882g/cm3, 1.486, 0.018%, 6.24cP, 148°C, 51...

Comparatives Study of Production Biodiesel from Soybean oil and Jatropha Curcas Seeds Oil

This study involves transesterification of soybean and Jatrophaoils with methanol, using sodium hydroxide as the catalyst to producedbiodiesel as an alternative to petroleum diesel. This work investigatesthe effects of temperature and time on the production of biodiesel fromthe feed stocks employed. Also investigated are the effects of particlesize and temperature on the production of oil from the Jatropha seed.The produced biodiesels from soybean and Jatropha oil were character-ised to determine their suitability as a replacement for the petrol diesel.Results obtained shows that both temperature and time influence theproduction of biodiesel from the soybean and Jatropha oil. Analyses ofthe produced biodiesels also indicates that the properties of the biodie-sels produced shows that the density, refractive index, moisture content,viscosity, flash point, cetane number, pour point and sulphur content ofthe biodiesel produced from soybean oil are 0.882g/cm3, 1.486, 0.018%,6.24cP, 148°C, 51.3, –8.2 and 0.004% respectively. While the correspond-ing values of these properties for the biodiesel produced from Jatrophaoil are 0.861g/cm3, 1.532, 0.013%, 2.8cP, 89°C, 49.5, –7.9 and 0.001%. Itcan be inferred from the results on the properties of biodiesel that theproperties of the produced biodiesels from soybean and Jatropha oilsfit well within the set limits for the standard biodiesel and fossil diesel,the biodiesel can therefore be used as a replacement for the petrol diesel.Results of various analyses conducted on the biodiesels produced fromsoybean and Jatropha oil shows that biodiesel of good qualities can alsobe produced from the Jatropha oil and can be used as a substitute forproduction of biodiesel from soybean which is edible oil.

Effect of Calcination Temperature and MgO Crystallite Size on MgO/TiO2 Catalyst System for Soybean Transesterification

Effect of Calcination Temperature and MgO Crystallite Size on MgO/TiO2 Catalyst System for Soybean Transesterification

Soybean oil transesterification by the use of a microwave flow system

The production of methyl esters from soybean transesterification by the use of a microwave flow system has been investigated. A household microwave was modified as a biodiesel reactor for continuous transesterification. The effects of temperature at the exit point (50–110°C), the methanol/oil molar ratio (3:1, 6:1, 9:1 and 12:1) and the catalyst concentration (0.5%, 1.0% and 1.5% in weight of KOH) were evaluated. Final temperature depended on the reaction time, on the microwave power and on the reaction composition, mainly the methanol content. The obtained conversion was over 99% of methyl ester content, with a methanol/oil molar ratio of 12:1, a catalyst concentration of 1.0wt.% and a final temperature of 70°C (this temperature was arisen with 2min residence time and 200W of power). In order to compare, the conventional heating systems were also employed in transesterification in homogeneous batch and flow processes. The transesterification reaction under microwave radiation yielded similar results but with very fast heating rates.

Transesterification of Soybean and Rice Bran Oil with Ethanol in a Continuous-Flow Microwave-Assisted System: Yields, Quality, and Reaction Kinetics

The use of microwaves as a heating medium to drive the transesterification of vegetable oils into ethyl esters was investigated. A continuous-flow microwave-assisted transesterification of soybean and rice bran oil was carried out in the presence of ethanol, using a molar ratio alcohol/oil of 5:1, and 0.6% w/w of sodium hydroxide as catalyst. The reactions were performed at atmospheric pressure, using a flow rate of 100 mL/min at temperatures of 50 and 73 °C for different reaction times (1, 5, and 10 min). At all tested parameters, the ethyl ester biodiesel produced conformed with ASTM specifications, with conversion rates between 96.7 and 99.3%, indicating a good quality biodiesel. The results indicated that microwave heating can be used effectively to obtain high ethyl esters of fatty acids (biodiesel) yields at lower alcohol/oil ratios, effectively reducing the reaction time, even under continuous-flow reactions due to a reduction in activation energy and an increase in Arrhenius pre-exponential factor. The results indicate that this heating process has potential to be scaled up for use in the industry to produce good quality biodiesel using ethanol as the alcohol of choice.

Nanosized and reusable SiO2/ZrO2 catalyst for highly efficient biodiesel production by soybean transesterification

Nanosized SiO2/ZrO2 catalyst with high surface area (131.50 ± 14 m2 g-1) was prepared by the sol-gel method. The material presented highly homogeneous particles with an average diameter of 250 nm according to SEM images. It was applied in the transesterification of soybean oil for biodiesel production. The biodiesel conversion reached a yield of 96.2 ± 1.4 % after 3 h of transesterification reaction catalised by SiO2/ZrO2 (SiZr). The catalyst was recovered and reused six times, maintaining a catalytic efficiency of about 84.1 %.

Simulation of Biodiesel Production through Transesterification of Vegetable Oils

Biodiesel can be produced from a number of natural, renewable sources, but vegetable oils are the main feedstocks. Most existing biodiesel plants currently rely upon the use of a homogeneous catalyst in a continuous reactor system, using the transesterification of soybean or rapeseed oil with methanol into alkyl esters. A key differentiation characteristic among the existing processes is that of the mixing pattern employed in the system. The present study compares reactor performances in terms of biodiesel yields for plug flow and complete mixing behaviors, along with the use of interstage phase separation. It is concluded that plug flow pattern shows a distinctive benefit in terms of yields and reactor volume reduction compared to complete mixing. Interstage separation improves the reacting system yields when proper phase separation can be achieved, maximizing glycerine removal from the downstream system. Staged mechanically stirred tank reactors can reach similar performances as plug flow behavior syste...

Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used in transesterification of soy bean and babassu oils – A new route for biodiesel syntheses

Catalysts of Cu(II) and Co(II) adsorbed in chitosan was used in transesterification of soy bean and babassu oils. The catalysts were characterized by infrared, atomic absorption and TG, and biodiesels was characterized by infrared, NMR, CG, TG, physic chemistry analysis. The maximum adsorption values found for copper and cobalt cations were 1.584 and 1.260mgg−1, respectively, in 180min. However, conversion of oils in biodiesel was better when used Co(II) adsorbed in chitosan.

Novel method for separating fatty esters from partial glycerides in biocatalytic transesterification of oils

Abstract Vegetable oil based partial glycerides have been synthesized by lipase catalyzed transesterification of soybean and linseed oil using different primary alcohols. A gel permeation chromatographic method has been used for monitoring the formation of partial glycerides in the transesterification step. A novel laboratory method has been developed for the separation of fatty esters from other partial glycerides by extending the transesterification reaction further by acryloylation/methacryloylation followed by free-radical polymerization. The fatty esters were thus selectively separated by removing the partial glycerides as polymers. Effect of type of lipase, solvent, temperature and substrate to nucleophile ratio in the transesterification step (step I) was also studied. The separation of butyl ester has been confirmed from the structural elucidation by 1H-NMR spectroscopy.

Chemoenzymatic synthesis and characterization of urethane oils for surface coatings

Two-step chemoenzymatic synthesis of urethane oils has been studied. Initially, the partial esters were prepared by lipase-catalyzed transesterification of soybean and linseed oils with n-butanol. Partial esters were further reacted with different diisocyanates to obtain urethane oils. The composition of the partial esters was varied with reaction time in the transesterification step. Among all the lipases, the lipozyme was found to be the most suitable lipase for the transesterification reaction, yielding 80–85%. All of the urethane oils were of low molecular weights irrespective of the type of oil used in their preparation. Urethane oils, based on MDI, exhibited the best scratch resistance. All of the urethane oils showed good acid and alkali resistance and excellent solvent resistance. These oils also satisfactorily passed the impact resistance and the flexibility tests.