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.     

Production of ethyl ester from crude palm oil by two-step reaction with a microwave system

The production of ethyl esters of fatty acids from a feed material of crude palm oil (CPO) with a high free fatty acid (FFA) content under microwave assistance has been investigated. Parametric studies have been carried out to investigate the optimum conditions for the esterification process (amount of ethanol, amount of catalyst, reaction time, and microwave power). As a result, a molar ratio of FFA to ethanol of 1:24 with 4% wt./wt. of H₂SO₄/FFA, a microwave power of 70 W, and a reaction time of 60 min have been identified as optimum reaction parameters for the esterification process aided by microwave heating. At the end of the esterification process, the amount of FFA had been reduced from 7.5 wt.% to less than 2 wt.%. Similar results were obtained following conventional heating at 70 °C, but only after a reaction time of 240 min. Transesterification of the esterified palm oil has been accomplished with a molar ratio of CPO to ethanol of 1:4, 1.5 wt.% KOH as a catalyst, a microwave power of 70 W, and a reaction time of 5 min. This two-step esterification and transesterification process provided a yield of 80 wt.% with an ester content of 97.4 wt.%. The final ethyl ester product met with the specifications stipulated by ASTM D6751-02.     

Biodiesel Production from Rubber Seed Oil by Transesterification Using a Co‐solvent of Fatty Acid Methyl Esters

Rubber seed oil (RSO) is a high‐potential feedstock for the production of biodiesel fuel (BDF) in Asia. Transesterification using fatty acid methyl esters (FAMEs) as co‐solvents was developed for BDF production from RSO with high content of free fatty acids (FFAs). The homogeneous system (FAMEs/triglyceride/methanol) was attained when the FAME content was more than 30 wt %. After esterification of RSO, the crude RSO obtained was transesterified with FAMEs as a co‐solvent. The quality of BDF with high FAME content satisfied the criteria of the EN 14214/JIS K2390 standards. These results suggest that FAMEs converted from FFAs can be applied as a co‐solvent and, thus, reused for BDF production.     

Optimization of rubber seed oil extraction using liquefied dimethyl ether

The objective of this study was to find the optimal condition for the extraction of rubber seed oil (RSO), using liquefied dimethyl ether (DME). Response surface methodology with a spherical central composite design model was employed to determine the optimal extraction condition, consisting of a seed moisture content (%wt), a solvent to solid ratio (g/g), and an extraction temperature (°C). A quadratic regression equation suggested the optimal extraction condition was a moisture content of 56.4%wt, a solvent to solid ratio of 6.7 (g/g), and a temperature of 33.3?°C. At this condition, the RSO yield predicted by the model gave a slight deviation of 0.68% from the experimentally validated results (41.48 versus 41.20%). RSO has a kinematic viscosity of 36.8 cSt, an acid value of 10.7 KOH/g oil, a fatty acid content of 5.1% and an unsaturated fatty acid content of 80%, resulting in the potential production of biodiesel, biolubricants, and biodegradable plastics.     

Biodiesel production from vegetable oil using heterogenous acid and alkali catalyst

Zanthoxylum bungeanum seed oil (ZSO) with high free fatty acids (FFA) can be used for biodiesel production by ferric sulfate-catalyzed esterification followed by transesterification using calcium oxide (CaO) as an alkaline catalyst. Acid value of ZSO with high FFA can be reduced to less than 2 mg KOH/g by one-step esterification with methanol-to-FFA molar ratio 40.91:1, ferric sulfate 9.75% (based on the weight of FFA), reaction temperature 95 °C and reaction time 2 h, which satisfies transesterification using an alkaline catalyst. The response surface methodology (RSM) was used to optimize the conditions for ZSO biodiesel production using CaO as a catalyst. A quadratic polynomial equation was obtained for biodiesel conversion by multiple regression analysis and verification experiments confirmed the validity of the predicted model. The optimum combination for transesterification was methanol-to-oil molar ratio 11.69:1, catalyst amount 2.52%, and reaction time 2.45 h. At this optimum condition, the conversion to biodiesel reached above 96%. This study provided a practical method to biodiesel production from raw feedstocks with high FFA with high reaction rate, less corrosion, less toxicity, and less environmental problems.     

Kinetics of methyl ester production from mixed crude palm oil by using acid-alkali catalyst

The production of biodiesel from high free fatty acid mixed crude palm oil using a two-stage process was investigated. The kinetics of the reactions was determined in a batch reactor at various reaction temperatures. It was found that the optimum conditions for reducing high free fatty acid (FFA) in MCPO (8-12 wt.%/wt oil) using esterification was a 10:1 molar ratio of methanol to FFA and using 10 wt.%/wt of sulfuric acid (based on FFA) as catalyst. The subsequent transesterification reaction to convert triglycerides to the methyl ester was found to be optimal using 6:1 molar ratio of methanol to the triglyceride (TG) in MCPO and using 0.6 wt.%/vol_TG sodium hydroxide as catalyst. Both reactions were carried out in a stirred batch reactor over a period of 20 min at 55, 60 and 65 °C. The concentration of compounds in each sample was analyzed by Thin Layer Chromatography/Flame Ionization Detector (TLC/FID), Karl Fischer, and titration techniques. The results were used for calculating the rate coefficients by using the curve-fitting tool of MATLAB. Optimal reaction rate coefficients for the forward and reverse esterification reactions of FFA were 1.340 and 0.682 l mol⁻¹ min⁻¹, respectively. The corresponding optimal transesterification, rate coefficients for the forward reactions of TG, diglyceride (DG), and monoglyceride (MG) of transesterification were 2.600, 1.186, and 2.303 l mol⁻¹ min⁻¹, and for the reverse reactions were 0.248, 0.227, and 0.022 l mol⁻¹ min⁻¹, respectively.     

Biodiesel production from high FFA rubber seed oil

Currently, most of the biodiesel is produced from the refined/edible type oils using methanol and an alkaline catalyst. However, large amount of non-edible type oils and fats are available. The difficulty with alkaline-esterification of these oils is that they often contain large amounts of free fatty acids (FFA). These free fatty acids quickly react with the alkaline catalyst to produce soaps that inhibit the separation of the ester and glycerin. A two-step transesterification process is developed to convert the high FFA oils to its mono-esters. The first step, acid catalyzed esterification reduces the FFA content of the oil to less than 2%. The second step, alkaline catalyzed transesterification process converts the products of the first step to its mono-esters and glycerol. The major factors affect the conversion efficiency of the process such as molar ratio, amount of catalyst, reaction temperature and reaction duration is analyzed. The two-step esterification procedure converts rubber seed oil to its methyl esters. The viscosity of biodiesel oil is nearer to that of diesel and the calorific value is about 14% less than that of diesel. The important properties of biodiesel such as specific gravity, flash point, cloud point and pour point are found out and compared with that of diesel. This study supports the production of biodiesel from unrefined rubber seed oil as a viable alternative to the diesel fuel.     

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.     

Thermal dehydrochlorination of PVC in the presence of rubber seed oil

Dehydrochlorination rates of PVC in nitrogen atmosphere were determined in the presence of rubber seed oil (RSO), epoxidized rubber seed oil (ERSO), barium soap of rubber seed oil fatty acids and barium soap of epoxidized fatty acid of rubber seed oil. The initial rates of dehydrochlorination and the time required for the degradation to attain 1% conversion showed that the rubber seed oil derivatives exert a stabilizing effect on the degradation of PVC. The order of the stabilizing effect was found to be metal soaps of ERSO < metal soaps of RSO < ERSO < RSO.     

Biodiesel production from non-degummed vegetable oils: Phosphorus balance throughout the process

In this work, the biodiesel production process using high-phosphorous content raw materials is studied. The objective is to determine the phosphorous mass balances, in order to determine the amount of this element in each stream of an integrated process including esterification, transesterification, and glycerin purification. It was found that up to 97% of the initial phosphorous content in the oil is accumulated in the glycerin phase. The small amount of phosphorous left in the biodiesel phase after decantation is eliminated during the acid extraction carried out to purify the biodiesel. The evaporation of methanol after the reaction plays a major role in the quantity of phosphorous and soaps left in the biodiesel phase. For example, with a crude soybean oil containing 226 ppm of phosphorous, the methanol content at the end of the reaction in the biodiesel phase is 4.6 wt.%, being the phosphorous content 7.1 ppm, and the soap concentration 3.89 g/kg. The methanol was evaporated in such a way that its concentration dropped to 0.35 wt.%, and the phosphorous and soaps concentrations decreased to 4 ppm and 0.7 g/kg respectively. This has a direct impact in the quality of the final biodiesel. During the esterification, also an important amount of phosphorous is eliminated from the biodiesel phase.     

Statistical optimization for biodiesel production from waste frying oil through two-step catalyzed process

The aim of this work was to investigate the optimum conditions in biodiesel production from waste frying oil using two-step catalyzed process. In the first step, sulfuric acid was used as a catalyst for the esterification reaction of free fatty acid and methanol in order to reduce the free fatty acid content to be approximate 0.5%. In the second step, the product from the first step was further reacted with methanol using potassium hydroxide as a catalyst. The Box-Behnken design of experiment was carried out using the MINITAB RELEASE 14, and the results were analyzed using response surface methodology. The optimum conditions for biodiesel production were obtained when using methanol to oil molar ratio of 6.1:1, 0.68 wt.% of sulfuric acid, at 51 °C with a reaction time of 60 min in the first step, followed by using molar ratio of methanol to product from the first step of 9.1:1, 1 wt.% KOH, at 55 °C with a reaction time of 60 min in the second step. The percentage of methyl ester in the obtained product was 90.56 ± 0.28%. In addition, the fuel properties of the produced biodiesel were in the acceptable ranges according to Thai standard for community biodiesel.     

Preparation, analysis and applications of rubber seed oil and its derivatives in surface coatings

Rubber seed oil (RSO) and its derivatives, heated rubber seed oil (HRSO) and alkyd resins were evaluated as binders in air drying solvent and waterborne coatings. HRSO was obtained by heating RSO at 300±5°C until the desired viscosity. Acid value of RSO (53) is somewhat high. The major saturated fatty acids are palmitic (10.2%) and stearic (8.7%) while the main unsaturated fatty acids are oleic (24.6%), linoleic (39.6%) and linolenic (16.3%). Naturally, RSO is semi-drying and heating enhances its drying ability. GPC analysis reveals that RSO consists of a rather high molecular weight fraction that is rarely found in commonly known vegetable oils. The average molecular weight of RSO is higher than that of HRSO with the latter narrower in molecular weight distribution. Low molecular weight species constitute greater proportion of the alkyds and their number average molecular weights range between 1379 and 3304 which are comparable to those of commercial alkyds. The narrower the size distribution the better the quality of these alkyds as binders. Physico-chemical properties of solvent-borne alkyds vary with oil length (OL) and they are optimum at 50% OL. Water-borne alkyds investigated show that the sample with lower oil content contains lower volatile organic content. All the alkyd samples and HRSO are fairly resistant to water and alkali while they are virtually unaffected by acid and salt solutions. However, samples IV and V (water-borne alkyds) are more resistant than their solvent-borne counterparts (samples I–III) but exhibited lower scratch/gouge pencil hardness.     

An ideal feedstock, kusum (Schleichera triguga) for preparation of biodiesel: Optimization of parameters

Kusum (Schleichera triguga), a non-edible oil bearing plant has been used as an ideal feedstock for biodiesel development in the present study. Various physical and chemical parameters of the raw oil and the fatty acid methyl esters derived have been tested to confirm its suitability as a biodiesel fuel. The fatty acid component of the oil was tested by gas chromatography. The acid value of the oil was determined by titration and was found to 21.30 mg KOH/g which required two step transesterification. Acid value was brought down by esterification using sulfuric acid (H₂SO₄) as a catalyst. Thereafter, alkaline transesterification was carried out using potassium hydroxide (KOH) as catalyst for conversion of kusum oil to its methyl esters. Various parameters such as molar ratio, amount of catalyst and reaction time were optimized and a high yield (95%) of biodiesel was achieved. The high conversion of the feedstock into esters was confirmed by analysis of the product on gas chromatograph-mass spectrometer (GC-MS). Viscosity and acid value of the product biodiesel were determined and found to be within the limits of ASTM D 6751 specifications. Elemental analysis of biodiesel showed presence of carbon, hydrogen, oxygen and absence of nitrogen and sulfur after purification. Molar ratio of methanol to oil was optimized and found to be 10:1 for acid esterification, and 8:1 for alkaline transesterification. The amounts of H₂SO₄ and KOH, 1% (v/v) and 0.7% (w/w), respectively, were found to be optimum for the reactions. The time duration of 1 h for acid esterification followed by another 1 h for alkaline transesterification at 50 ± 0.5 °C was optimum for synthesis of biodiesel.     

A hybrid feedstock for a very efficient preparation of biodiesel

Biodiesel has been synthesized from karanja, mahua and hybrid {karanja and mahua (50:50 v/v)} feedstocks. A high yield in the range of 95-97% was obtained with all the three feedstocks. Conversion of vegetable oil to fatty acid methyl esters was found to be 98.6%, 95.71% and 94% for karanja, mahua and hybrid feedstocks respectively. The optimized reaction parameters were found to be 6:1 (methanol to oil) molar ratio, H₂SO₄ (1.5% v/v), at 55 ± 0.5 °C for 1 h during acid esterification for the three feedstocks. During alkaline transesterification, a molar ratio of 8:1 (methanol to oil), 0.8 wt.% KOH (wt/wt) at 55 ± 0.5 °C for 1 h was found to be optimum to achieve high yield for karanja oil. For mahua oil and the hybrid feedstock, 6:1 (methanol to oil) molar ratio, 0.75 (w/w) KOH at 55 ± 0.5 °C for 1 h was optimum for alkaline transesterification to obtain a high yield. High yield and conversion from hybrid feedstock during transesterification reaction was an indication that the reaction was not selective for any particular oil. ¹H NMR has been used for the determination of conversion of the feedstock to biodiesel.     

Effect of low frequency ultrasonic assisted extraction on the quality of seed oils of Indian origin

The study gives an insight into the effect of low frequency ultrasonic enhancement of solvent extraction on the quality of non-edible oils (Jatropha and Pongamia as model seed varieties) in comparison to conventional methods of extraction i.e. direct reflux or soxhlet extraction using hexane. A series of experiments have been carried out to study the effect of variables; solute to solvent ratio (1:2.5-1:10) and reaction time (30 s-60 min) on the yield of oil. The quality of oil extracted by different methods have been assessed by determining the acid value of oil by ASTM D-974/04 method, a measurement of triglyceride and fatty acid degradation, by the presence of phorbol esters in Jatropha curcas and phenolic compounds in Pongamia oil analyzed using HPLC. Under optimized conditions solute to solvent ratio of 1:10 (w/v), 3 min extraction time yields > 95% pure oil having < 1% FFA in Jatropha curcas and 30 s extraction time in Pongamia seed yields oil with less than 2% FFA in comparison to conventional method of extraction in 16 h.     

Biodiesel production from tobacco (Nicotiana tabacum L.) seed oil with a high content of free fatty acids

The production of fatty acid methyl esters (FAME) from crude tobacco seed oil (TSO) having high free fatty acids (FFA) was investigated. Due to its high FFA, the TSO was processed in two steps: the acid-catalyzed esterification (ACE) followed by the base-catalyzed methanolysis (BCM). The first step reduced the FFA level to less than 2% in 25 min for the molar ratio of 18:1. The second step converted the product of the first step into FAME and glycerol. The maximum yield of FAME was about 91% in about 30 min. The tobacco biodiesel obtained had the fuel properties within the limits prescribed by the latest American (ASTM D 6751-02) and European (DIN EN 14214) standards, except a somewhat higher acid value than that prescribed by the latter standard (<0.5). Thus, tobacco seeds (TS), as agricultural wastes, might be a valuable renewable raw material for the biodiesel production.     

Biodiesel production from Croton megalocarpus oil and its process optimization

Production of biodiesel from non-edible feedstocks is attracting more attention than in the past, for the purpose of manufacturing alternative fuels without interfering with the food chain. Biodiesel was produced using Croton megalocarpus oil as a non-edible feedstock. C. megalocarpus oil was obtained from north Tanzania. This study aimed at optimizing the biodiesel production process parameters experimentally. The parameters involved in the optimization process were the amount of the catalyst, of alcohol, temperature, agitation speed and reaction time. The optimum biodiesel conversion efficiency obtained was 88% at the optimal conditions of 1.0 wt.% amount of potassium hydroxide catalyst, 30 wt.% amount of methanol, 60 °C reaction temperature, 400 rpm agitation rate and 60 min reaction time. The properties of croton biodiesel which were determined fell within the recommended biodiesel standards. Croton oil was found with a free fatty acid content of 1.68% which is below the 2% recommended for the application of the one step alkaline transesterification method. The most remarkable feature of croton biodiesel is its cold flow properties. This biodiesel yielded a cloud and pour point of −4 °C and −9 °C, respectively, while its kinematic viscosity lay within the recommended standard value. This points to the viability of using croton biodiesel in cold regions.     

Biodiesel production from waste animal fats using pyrolysis method

It is necessary to utilize waste cooking oil as a raw material of biodiesel because the land area available for cultivation in Japan is limited. Waste cooking oil also includes long-chain saturated compounds and free fatty acids derived from animal fats. The former has a high freezing point and the latter forms a soap with the alkali catalyst typically used in biodiesel production, reducing the yield. To make waste cooking oil available for biodiesel production, pyrolysis of the waste oil was attempted. The resulting triacylglycerols were found to decompose at 360 to 390 °C, fatty acids were generated by cleavage of the ester bond, and short-chain hydrocarbons and short-chain fatty acids were generated by cleavage of the unsaturated bonds in the hydrocarbon chain. When the retention time was extended with a reaction temperature of 420 °C, light-oil hydrocarbons were generated by decarboxylation of the fatty acids. By adding palladium supported by activated carbon (Pd/C) as a catalyst, decarboxylation was promoted, and hydrocarbons comparable to light oil were selectively obtained in high yield at 85 wt.%. Compared to the biodiesel obtained by transesterification, the biodiesel obtained by pyrolysis showed improvement of about − 5 °C in the pseudo-cold filter plugging point.     

Characterization of Oil Precipitate and Oil Extracted from Condensed Corn Distillers Solubles

Oil extracted from condensed corn distillers solubles (CCDS) can form a semi-solid and waxy precipitate at the bottom of containers during storage. CCDS is a good source to recover oil, and such oil can be converted to biodiesel. Precipitate formation in the extracted oil is mainly a physical stability problem, but it may become a performance problem for biodiesel. The objective of the present work was to determine the composition of the CCDS oil precipitate and also determine if valuable phytosterols were present in high concentration. The free fatty acid (FFA) content was very high, 35.7%, and fatty acid composition of the FFA fraction was predominantly palmitic acid, 70.3%. The solid appearance was mainly due to a high percentage of high-melting point free saturated fatty acid. The total unsaponifiable matter was 2.0%, and total phytosterol content was 8.6 mg/g of CCDS oil precipitate. Therefore, CCDS oil precipitate is a not an enriched source of phytosterols compared to total sterols present in crude corn oil (15.6 mg/g oil). The wax content was high, 2.5 mg/g of CCDS oil precipitate compared to 0.5 mg/g of crude corn oil. CCDS oil that is uncentrifugable but polar solvent extractable (trapped oil fraction) was also characterized and found to contain more polar lipids than those in the free oil fraction (centrifugable oil).     

Studies on improving the performance of rubber seed oil fuel for diesel engine with DEE port injection

Use of vegetable oils in diesel engines leads to a marginally inferior performance and higher smoke emissions due to their high viscosity and carbon residue. The performance of vegetable oils can be improved by injecting a small quantity of diethyl ether (DEE) along with air. The main objective of this study is to improve the performance, emission and combustion characteristics of a direct injection diesel engine fuelled with rubber seed oil (RSO) through DEE injection at different flow rates of 100, 150 and 200 g/h. A single cylinder diesel engine with rated output of 4.4 kW at 1500 rpm was converted to operate in the DEE injection mode. DEE was injected into the intake port during suction stroke, while rubber seed oil was injected directly inside the cylinder at the end of compression stroke. The injection timing of DEE was optimized for this mode of operation. Results indicate that the brake thermal efficiency of the engine improves from 26.5% with neat RSO to a maximum of 28.5% with DEE injection rate of 200 g/h. Smoke reduces from 6.1 to 4 BSU with DEE injection at the maximum efficiency flow rate. Hydrocarbon and carbon monoxide emissions are also less with DEE injection. There is an increase in the NO_x emission from 6.9 g/kWh to 9.3 g/kWh at the optimum DEE flow rate. DEE injection with RSO shows higher peak pressure and rate of pressure rise compared to neat RSO. Heat release rate indicates an increase in the combustion rate due to the reduced ignition delay and combustion duration with DEE injection.