Reactive extraction and in situ esterification of Jatropha curcas L. seeds for the production of biodiesel

Jatropha curcas L. has recently been hailed as the promising feedstock for biodiesel production as it does not compete with food sources. Conventional production of biodiesel from J. curcas L. seeds involve two main processing steps; extraction of oil and subsequent esterification/transesterification to fatty acid methyl esters (FAME). In this study, the feasibility of in situ extraction, esterification and transesterification of J. curcas L. seeds to biodiesel was investigated. It was found that the size of the seed and reaction period effect the yield of FAME and amount of oil extracted significantly. Using seed with size less than 0.355 mm and n-hexane as co-solvent with the following reaction conditions; reaction temperature of 60 °C, reaction period of 24 h, methanol to seed ratio of 7.5 ml/g and 15 wt% of H₂SO₄, the oil extraction efficiency and FAME yield can reached 91.2% and 99.8%, respectively. This single step of reactive extraction process therefore can be a potential route for biodiesel production that reduces processing steps and cost.     

Continuous enzymatic production of biodiesel from virgin and waste sunflower oil in supercritical carbon dioxide

A continuous process for biodiesel production in supercritical carbon dioxide was implemented. In the transesterification of virgin sunflower oil with methanol, Lipozyme TL IM led to fatty acid methyl esters yields (FAME) that exceeded 98% at 20 MPa and 40 °C, for a residence time of 20 s and an oil to methanol molar ratio of 1:24. Even for moderate reaction conversions, a fractionation stage based on two separators afforded FAME with >96% purity. Lipozyme TL IM was less efficient with waste cooking sunflower oil. In this case, a combination of Lipozyme TL IM and Novozym 435 afforded FAME yields nearing 99%.     

Continuous production of fatty acid methyl esters from corn oil in a supercritical carbon dioxide bioreactor

Continuous production of fatty acid methyl esters (FAMEs) from corn oil was studied in a supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Response surface methodology (RSM) based on central composite rotatable design (CCRD) was employed to investigate and optimize the reaction conditions: pressure (11-35 MPa), temperature (35-63 °C), substrate mole ratio (methanol:corn oil 1-9) and CO₂ flow rate (0.4-3.6 L/min, measured at ambient conditions). Increasing the substrate mole ratio increased the FAME content, whereas increasing pressure decreased the FAME content. Higher conversions were obtained at higher and lower temperatures and CO₂ flow rates compared to moderate temperatures and CO₂ flow rates. The optimal reaction conditions generated from the predictive model for the maximum FAME content were 19.4 MPa, 62.9 °C, 7.03 substrate mole ratio and 0.72 L/min CO₂ flow rate. The optimum predicted FAME content was 98.9% compared to an actual value of 93.3 ± 1.1% (w/w). The SC-CO₂ bioreactor packed with immobilized lipase shows great potential for biodiesel production.     

Transesterification of sunflower oil in a countercurrent trickle-bed reactor packed with a CaO catalyst

Transesterification of sunflower oil with methanol to form biodiesel was performed in a countercurrent trickle-bed reactor, using calcium oxide particles 1-2 mm in diameter as a packed, solid base catalyst. Although biodiesel production generally requires a reaction temperature below the boiling point of methanol to maintain a heterogeneous, liquid-liquid reaction, in the present study the reaction temperature was varied from 80 to 140 °C to confirm the progress of transesterification in a gas-liquid-solid phase reaction system. Oil droplets released from a thin tube flowed downward, while vaporized methanol flowed upward in the bed. The effects of the reaction temperature, methanol and oil flow rates, and the bed height on the FAME yield were investigated. The oil residence time in the reactor, which was controlled by changing both the oil flow rate and the bed height, had a significant effect on the FAME yield. In addition, the FAME yield increased with reaction temperature and was maximal at 373 K due to the change in residence time associated with reduced oil viscosity at higher temperatures. The FAME yield was 98% at a reaction temperature of 373 K when the methanol and oil flow rates were 3.8 and 4.1 mL/h, respectively.     

Dolomite as a heterogeneous catalyst for transesterification of canola oil

In this study, the catalytic activity of dolomite was evaluated for the transesterification of canola oil with methanol to biodiesel in a heterogeneous system. The influence of the calcination temperature of the catalyst and the reaction variables such as the temperature, catalyst amount, methanol/canola oil molar ratio, and time in biodiesel production were investigated. The maximum activity was obtained with the catalyst calcined at 850 °C. When the reaction was carried out at reflux of methanol, with a 6:1 molar ratio of methanol to canola oil and a catalyst amount of 3 wt.% the highest FAME yield of 91.78% was obtained after 3 h of reaction time.     

In situ production of fatty acid methyl ester from low quality rice bran: An economical route for biodiesel production

Low quality rice bran was used to produce fatty acid methyl ester (FAME) via in situ extraction, esterification and transesterification process. The effects of the acid and alkaline catalysts on the ester yield, esterification and transesterification process were studied. When 75 ml of absolute methanol, 150 ml of petroleum ether, 0.75 g of concentrated sulfuric acid and 0.71 g of sodium hydroxyl were used, 16.69% (w_FAME/w_{rice bran}) of FAME was obtained. The esterification rate and the transesterification rate reached 98.83% and 80.47%. Based on the proposed route, the production process of FAME (biodiesel) could be simplified and the production cost could be reduced.     

Glycerol removal from biodiesel using membrane separation technology

Membrane separation technology was used to remove free glycerol from biodiesel in order to meet the ASTM D6751 and EN 14214 standards. Fatty acid methyl esters (FAME) produced from canola oil and methanol were purified using ultra-filtration. The effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was studied. A modified polyacrylonitrile (PAN) membrane, with 100 kD molecular weight cut-off was used in all runs. Tests were performed at 25 °C and 552 kPa operating pressure. The free glycerol content in the feed, retentate and permeate of the membrane system was analyzed using gas chromatography according to ASTM D6584. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME even at approx. 0.08 mass%. This is four orders of magnitude less than the amount of water required in a conventional biodiesel purification process using water washing. It is suggested that the mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated FAME. This was confirmed by the presence of particulates in the untreated FAME. The size of the particles and the free glycerol separation both increased with increasing water content of the FAME. The trends of separation and particle size vs. water content in the FAME phase were very similar and exhibited a sudden increase at 0.08 mass% water in the untreated FAME. This supports the conclusion that water increased the size of the distributed glycerol phase in the untreated FAME leading to its separation by the ultra-filtration membrane. The technology for the removal of free glycerol from biodiesel was found to use 2.0 g of water per L of treated FAME (0.225 mass% water) vs. the current 10 L of water per L of treated FAME.     

Transesterification of vegetable oil to biodiesel fuel using alkaline catalyst

Biodiesel is gaining more and more importance as an attractive fuel due to the depleting fossil fuel resources. Chemically biodiesel is monoalkyl esters of long chain fatty acids derived from renewable feed stock like vegetable oils and animal fats. It is produced by transesterification in which, oil or fat is reacted with a monohydric alcohol in presence of a catalyst to give the corresponding monoalkyl esters. This article reports experimental data on the production of fatty acid methyl esters from vegetable oils, soybean and cottonseed oils using sodium hydroxide as alkaline catalyst. The variables affecting the yield and characteristics of the biodiesel produced from these vegetable oils were studied. The variables investigated were reaction time (1-3 h), catalyst concentration (0.5-1.5 w/wt%), and oil-to-methanol molar ratio (1:3-1:9). From the obtained results, the best yield percentage was obtained using a methanol/oil molar ratio of 6:1, sodium hydroxide as catalyst (1%) and 60 ± 1 °C temperature for 1 h. The yield of the fatty acid methyl ester (FAME) was determined according to HPLC. The composition of the FAME was determined according to gas chromatography. The biodiesel samples were physicochemically characterized. From the results it was clear that the produced biodiesel fuel was within the recommended standards of biodiesel fuel.     

Roselle (Hibiscus sabdariffa L.) oil as an alternative feedstock for biodiesel production in Thailand

The production of biodiesel fuel from crude roselle oil was evaluated in this study. The process of alkali-catalyzed transesterification with methanol was carried out to examine the effects of reaction variables on the formation of methyl ester: variables which included methanol-to-oil molar ratios of 4:1-10:1, catalyst concentrations of 0.25-2.0% w/w of oil, reaction temperatures of 32-60 °C, and reaction times of 5-80 min. The methyl ester content from each reaction condition was analyzed by gas chromatography (GC), the optimum condition having been achieved at a methanol-to-oil molar ratio of 8:1, a catalyst concentration of 1.5% w/w of oil, a reaction temperature of 60 °C, and a reaction time of 60 min. The resultant methyl ester content of 99.4% w/w, plus all of the other measured properties of the roselle biodiesel, met the Thai biodiesel (B100) specifications and international standards EN 14214:2008 (E) and ASTM D 6751-07b, with the exception of a higher carbon residue and lower oxidation stability.     

Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application to biodiesel production

In order to study solid base catalyst for biodiesel production with environmental benignity, transesterification of edible soybean oil with refluxing methanol was carried out in the presence of calcium oxide (CaO), -hydroxide (Ca(OH)₂), or -carbonate (CaCO₃). At 1 h of reaction time, yield of FAME was 93% for CaO, 12% for Ca(OH)₂, and 0% for CaCO₃. Under the same reacting condition, sodium hydroxide with the homogeneous catalysis brought about the complete conversion into FAME. Also, CaO was used for the further tests transesterifying waste cooking oil (WCO) with acid value of 5.1 mg-KOH/g. The yield of FAME was above 99% at 2 h of reaction time, but a portion of catalyst changed into calcium soap by reacting with free fatty acids included in WCO at initial stage of the transesterification. Owing to the neutralizing reaction of the catalyst, concentration of calcium in FAME increased from 187 ppm to 3065 ppm. By processing WCO at reflux of methanol in the presence of cation-exchange resin, only the free fatty acids could be converted into FAME. The transesterification of the processed WCO with acid value of 0.3 mg-KOH/g resulted in the production of FAME including calcium of 565 ppm.     

Optimization of the transesterification reaction in biodiesel production

In this paper response surface methodology (RSM) was used to study the transesterification reaction of rapeseed oil for biodiesel production. The three main factors that drive the conversion of triglycerides into fatty acid methyl esters (FAME) were studied according to a full factorial design at two levels. These factors were catalyst concentration (KOH), temperature and reaction time. The range investigated for each factor was selected taking into account the process of Fox Petroli S.p.A. Analysis of variance (ANOVA) was used to determine the significance of the factors and their interactions which primarily affect the first of the two transesterification stages. This analysis evidenced the best operating conditions of the first transesterification reaction performed at Fox’s plant: KOH concentration 0.6% w/w, temperature 50 °C and reaction time 90 min with a CH₃OH to KOH ratio equal to 60. Three empirical models were derived to correlate the experimental results, suitable to predict the behavior of triglyceride, diglyceride and monoglyceride concentration. These models showed a good agreement with the experimental results, demonstrating that this methodology may be useful for industrial process optimization.     

Production of biodiesel through optimized alkaline-catalyzed transesterification of rapeseed oil

Present work reports an optimized protocol for the production of biodiesel through alkaline-catalyzed transesterification of rapeseed oil. The reaction variables used were methanol/oil molar ratio (3:1-21:1), catalyst concentration (0.25-1.50%), temperature (35-65 °C), mixing intensity (180-600 rpm) and catalyst type. The evaluation of the transesterification process was followed by gas chromatographic analysis of the rapeseed oil fatty acid methyl esters (biodiesel) at different reaction times. The biodiesel with best yield and quality was produced at methanol/oil molar ratio, 6:1; potassium hydroxide catalyst concentration, 1.0%; mixing intensity, 600 rpm and reaction temperature 65 °C. The yield of the biodiesel produced under optimal condition was 95-96%. It was noted that greater or lower the concentration of KOH or methanol than the optimal values, the reaction either did not fully occur or lead to soap formation.The quality of the biodiesel produced was evaluated by the determinations of important properties such as density, specific gravity, kinematic viscosity, higher heating value, acid value, flash point, pour point, cloud point, combustion point, cold filter plugging point, cetane index, ash content, sulphur content, water content, copper strip corrosion value, distillation temperature and fatty acid composition. The produced biodiesel was found to exhibit fuel properties within the limits prescribed by the latest American Standards for Testing Material (ASTM) and European EN standards.     

Prospects of non-catalytic supercritical methyl acetate process in biodiesel production

Conventional biodiesel production methods utilize alcohol as acyl acceptor and produces glycerol as side product. Hence, with escalating production of biodiesel throughout the world, it leads to oversupply of glycerol and subsequently causes devaluation in the market. In this study, methyl acetate was employed as acyl acceptor in non-catalytic supercritical methyl acetate (SCMA) process to produce fatty acid methyl esters (FAME) and side product of triacetin, a valuable fuel additive instead of glycerol. Consequently, the properties of biodiesel produced (FAME and triacetin) are superior compared to conventional biodiesel method (FAME only). In this research, the effects of reaction temperature, reaction time and molar ratio of methyl acetate to oil on the yield of biodiesel were investigated. Apart from that, the influence of impurities commonly found in waste oils/fats such as free fatty acids and water were studied as well and compared with methanol-based reactions of supercritical and heterogeneous catalysis. Results show that biodiesel yields in SCMA process could achieve 99 wt.% when the operating conditions were fixed at 400 °C/220 bar for reaction temperature, methyl acetate/oil molar ratio of 30:1 and 60 min of reaction time. Furthermore, SCMA did not suffer from adverse effect with the presence of impurities, proving that SCMA has a high tolerance towards contamination which is crucial to allow the utilization of inexpensive waste oils/fats as biodiesel feedstock.     

Transesterification of vegetable oil to biodiesel fuel using acid catalysts in the presence of dimethyl ether

The immiscibility of methanol and vegetable oil leads to a mass-transfer resistance in the transesterification of vegetable oil. To overcome this problem, dimethyl ether (DME) was used as an environmentally friendly cosolvent to produce a homogeneous solution. Methylesterifications of corn oil in both the presence and the absence of DME were performed using p-toluenesulfonic acid (PTSA), benzenesulfonic acid and sulfuric acid. PTSA showed highest catalytic activity. The yield of FAME reached 97.1% when 4 wt% of PTSA based on the oil weight was used at 80 °C with a reaction time of 2 h in the presence of DME. The obtained biodiesel was composed of methyl palmitate (9.1 wt%), methyl oleate (33.9 wt%), methyl linoleate (53.5 wt%), methyl linolenate (3.0 wt%) and methyl arachidate (0.5 wt%), and it was similar to the biodiesel compositions from corn oil as reported. The effects of concentrations of FFA and water on FAME yields were also investigated. All results suggested that the reaction rate was greatly improved by the addition of DME to the reaction system.     

Separation of glycerol from FAME using ceramic membranes

International standards (e.g., ASTM D6751 and EN14214) limit the presence of free glycerol in biodiesel. The traditional water wash method for removing glycerol from crude fatty acid methyl esters (FAME) obtained in the production of biodiesel results in waste waters that cannot be readily discharged. To circumvent the water wash purification method, a membrane separation system using ceramic membranes was designed, constructed and tested for the removal of glycerol from crude FAME from a biodiesel production process. Ceramic membranes in the ultrafiltration (0.05 μm) and microfiltration (0.2 μm) ranges were tested at three different operating temperatures: 0, 5 and 25 °C. All runs separated glycerol from the crude FAME. International standards for glycerol content in biodiesel were met after 3 h when utilizing the ultrafiltration membrane setup at 25 °C with a concentration factor greater than 1.6.     

Transesterification of palm oil on KyMg1 − xZn1 + xO3 catalyst: Effect of Mg-Zn interaction

The Mg-Zn interaction effect of K_yMg_1 − xZn_1 + xO₃ heterogeneous type catalyst and its performance on transesterification of palm oil have been studied using the response surface methodology and the factorial design of experiments. The catalyst was synthesized using the co-precipitation method and the activity was assessed by transesterification of palm oil into fatty acid methyl esters. The ratio of the Mg/Zn metal interaction, temperature and time of calcination were found to have positive influence on the conversion of palm oil to fatty acid methyl ester (FAME) with the effect of metal to metal ratio and temperature of calcination being more significant. The catalytic activity was found to decrease at higher calcination temperature and the catalyst type K₂Mg_0.34Zn_1.66O₃ with Mg/Zn ratio of 4.81 gave FAME content of 73% at a catalyst loading of 1.404 wt.% of oil with molar ratio of methanol to oil being 6:1 at temperature of 150 °C in 6 h. A regression model was obtained to predict conversions to methyl esters as a function of metal interaction ratio, temperature of calcination and time. The observed activity of the synthesized catalyst was due to its synergetic structure and composition.     

Biodiesel production using supercritical methanol/carbon dioxide mixtures in a continuous reactor

Fatty acid methyl esters (biodiesel) were produced by the transesterification of triglycerides with compressed methanol (critical point at 240 °C and 81 bar) in the presence of solid acids as heterogeneous catalyst (SAC-13). Addition of a co-solvent, supercritical carbon dioxide (critical point at 31 °C and 73 bar), increased the rate of the supercritical alcohols transesterification, making it possible to obtain high biodiesel yields at mild temperature conditions. Experiments were carried out in a fixed bed reactor, and reactions were studied at 150-205 °C, mass flow rate 6-24 ml/min at a pressure of 250 bar. The molar ratio of methanol to oil, and catalyst amount were kept constant (9 g). The reaction temperature and space time were investigated to determine the best way for producing biodiesel. The results obtained show that the observed reaction rate is 20 time faster than conventional biodiesel production processes. The temperature of 200 °C with a reaction time of 2 min were found to be optimal for the maximum (88%) conversion to methyl ester and the free glycerol content was found below the specification limits.     

Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production

In this study, sulphuric acid (H₂SO₄) was used in the pretreatment of sludge palm oil for biodiesel production by an esterification process, followed by the basic catalyzed transesterification process. The purpose of the pretreatment process was to reduce the free fatty acids (FFA) content from high content FFA (> 23%) of sludge palm oil (SPO) to a minimum level for biodiesel production (> 2%). An acid catalyzed esterification process was carried out to evaluate the low content of FFA in the treated SPO with the effects of other parameters such as molar ratio of methanol to SPO (6:1-14:1), temperature (40-80 °C), reaction time (30-120 min) and stirrer speed (200-800 rpm). The results showed that the FFA of SPO was reduced from 23.2% to less than 2% FFA using 0.75% wt/wt of sulphuric acid with the molar ratio of methanol to oil of 8:1 for 60 min reaction time at 60 °C. The results on the transesterification with esterified SPO showed that the yield (ester) of biodiesel was 83.72% with the process conditions of molar ratio of methanol to SPO 10:1, reaction temperature 60 °C, reaction time 60 min, stirrer speed 400 rpm and KOH 1% (wt/wt). The biodiesel produced from the SPO was favorable as compared to the EN 14214 and ASTM D 6751 standard.     

FAME Production and Fatty Acid Profiles from Moist Chlorella sp. and Nannochloropsis oculata Biomass

In the present study, we investigated the production of fatty acid methyl esters (FAME) from moist Chlorella sp. and Nannochloropsis oculata biomass using a hydrolysis–esterification process. Additionally, we evaluated for the first time the fatty acid profile before and after this process. Hydrolysis of the lipid fraction was performed on a moist biomass in the presence of differing amounts of an acid catalyst in both 50 and 100 % w/w water relative to the biomass. The esterification of the crude extracts of the free fatty acids (FFA) was then investigated. The experiments show that in the presence of 50 % w/w water relative to the biomass, the hydrolysis–esterification process results in higher FFA and FAME yields. The analysis of the fatty ester profiles did not reveal any degradation of the FFA from the microalgae biomass under the hydrolysis–esterification conditions. The results were compared with both extraction–transesterification and direct transesterification processes using dry biomass. The extraction–transesterification and hydrolysis–esterification processes resulted in similar FAME yields and similar profiles of the fatty esters from dry and moist biomass materials, respectively.     

Transesterification of soybean oil with nano-MgO or not in supercritical and subcritical methanol

Nano-MgO can apparently improve the transesterification reaction of soybean oil with supercritical/subcritical methanol. The variables affecting the yield of methyl ester during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of methanol to soybean oil were investigated and compared with those of non-catalyst. When nano-MgO was added from 0.5 wt% to 3 wt%, the transesterification rate increased evidently, while the catalyst content was further enhanced to 5 wt%, little increased in yield. It was observed that increasing the reaction temperature had a favorable influence on methyl ester yield. In addition, for molar ratios of methanol to soybean oil ranging from 6 to 36, the higher molar ratios of methanol to oil was charged, the faster transesterification rate was obtained. When the temperature was increased to 533 K, the transesterification reaction was essentially completed within 10 min with 3 wt% nano-MgO and the methanol/oil molar rate 36:1. Such high reaction rate with nano-MgO was mainly owing to the lower activation energy (75.94 kJ/mol) and the higher stirring.