Development of biodiesel: Current scenario

Abstract Fuels are inevitable for industrial development and growth of any country. The life span of fossil fuel resources has always been terrifying. Biodiesel, a renewable source of energy seems to be an ideal solution for global energy demands including India as well. The current review is addressed to various aspects of biodiesel production. Latest literature has been critically reviewed and consulted. 5. Variables affecting the transesterification reaction Transesterification reaction is quite sensitive to various parameters. The reaction is either incomplete or the yield is reduced to a significant extent if the parameters are not optimised. These parameters include free fatty acids (FFAs), water content, molar ratio of alcohol to oil, catalyst, reaction temperature and stirring. Each parameter is equally important to achieve a high quality biodiesel which meets the regulatory standards. 5.1. Free fatty acids Free fatty acids (FFAs) are the saturated or unsaturated monocarboxylic acids that occur naturally in fats, oils or greases but are not attached to glycerol backbones [22]. Higher amount of free fatty acids leads to higher acid value. Vegetable oils should have free fatty acids within a desired limit for alkaline transesterification, beyond which either the reaction will not take place or the yield will be too less. Table 3 [7,18,23 – 27] depicts the level of FFA worked out by researchers. It is clear from the table that the FFA level in the oil should be below a desired level (ranging from less than 0.5% to less than 3%) for alkaline transesterification to take place. The application of the acid catalyst is to reduce the free fatty acids to a level safe enough for alkali transesterification. Else, the product formed will be soap instead of esters. During acid catalysed process, the FFA react with alcohol to produce esters but simultaneously, water is also produced which inhibits the transesterification reaction [28]. An alkali catalyst proceeds at around 4000 times faster than with the same amount of acid catalyst and hence is preferred over the acid catalyst after the acid value is reduced to the desired limit [29]. Hence, the transesterification reaction is one-step process for oils with FFA within the range and is a two-step process for oils with FFA exceeding the range. In a two-step process, acid esterification is followed by alkali transesterification.

5.2. Water content The raw materials being used as starting material should be free from water content. Water content as low as 0.1% has been reported to decrease the conversion of ester to a significant extent [28]. Srivastava and Verma [30] reported the removal of the moisture content by heating the oil in an oven for 1 h at 110°C before starting the transesterification reaction. Meher et al. [31] dissolved the catalyst, potassium hydroxide in methanol just before starting the transesterification reaction in an attempt to prevent the moisture absorbance. 5.3. Alcohol and molar ratio employed

Lower alcohols such as methanol, ethanol, propanol, etc. can be employed for transesterification reaction without any significant difference in the yield of the product. Methanol is toxic but is preferred among the others owing to its low cost. Ethanol is not preferred because of its low reactivity compared to methanol. Viscosity of ethyl esters is slightly higher and low temperature properties (cloud point, pour point) are slightly lower than those of methyl esters [32]. These findings make methanol more amenable for use as alcohol in biodiesel development. However, methanol has a lower boiling point of 64.7ºC and the transesterification reaction is carried out at a temperature which is near to this temperature. Vapours of methanol, which are highly toxic and can cause permanent blindness, are likely to be present near the site of reaction set up. Hence, appropriate measures have to be ensured for the safety of personnel working around. A new technique has been developed by the researchers [33] where alcohol in supercritical condition is used for the completion of transesterification reaction in shorter period of time without using any catalyst. The reason for the shorter time span is that the oil and supercritical alcohol exist in the same phase. In the supercritical transesterification method, a conversion of 50–95% was achieved in first 10 min. Presence of water was a source of interference in catalytic transesterification, whereas, the presence of water had shown a positive affect in methyl ester conversion by supercritical method [32]. The commonly employed molar ratio for two-step transesterification is 6:1 for acid transesterification and 9:1 for alkali catalyzed transesterification. However, the optimum molar ratio has shown to differ a little depending on the raw oil taken and its acid value. For single step transesterification reaction, 10:1 molar ratio has been used more often, although an optimum molar ratio varying from 6:1 to 13:1 has been employed by other researchers [34]. A molar ratio higher than the optimum value reduces the yield and makes the separation process of esters and glycerol difficult. High molar (40:1) is needed where supercritical methanol is used for transesterification method [33]. 5.4. Types and amount of catalysts A catalyst is needed to improve the transesterification reaction and yield [35]. Homogeneous catalyst has been in use at present at industrial level for production of biodiesel. Sulphuric acid (H2SO4) is the commonly used catalyst during acid transesterification whereas sodium hydroxide (NaOH) and potassium hydroxide (KOH) are the catalyst used for alkaline transesterification [34]. Sodium methoxide (CH3ONa) and potassium methoxide (CH3OK) are the other homogeneous catalyst which perform better than NaOH and KOH in terms of yield. Formation of small amount of water during the transesterification reaction results in lower yield of biodiesel with NaOH or KOH as a catalyst whereas CH3ONa or CH3OK show higher yield because there is no water formation as by-product during the reaction [36]. Among KOH and NaOH, Vicente et al. [37] reported higher yield with KOH (91.67%) as compared to that of NaOH (85.9%). However, the purity of the ester reported was similar with these two catalysts. Contrary to this, Leung and Guo [36] have reported different amounts of catalysts required to achieve the same conversion of methyl esters. The amounts of catalysts required were 1.1, 1.3 and 1.5 wt.% for NaOH, CH3ONa and KOH, respectively to get maximum conversion of methyl esters. This was attributed to the smallest molar mass of NaOH (40 g/mol) as compared to CH3ONa (54 g/mol) and KOH (56 g/mol). The amount of acid catalyst used to reduce the acid value ranges from 0.65% to 1.43% (v/v) H2SO4. However, the amount most commonly used by researchers is 1% (v/v) of 100% H2SO4. Optimum amount of H2SO4 as catalyst only is to be added, as higher volume may burn the oil and can darken the product. The amount of NaOH or KOH used during alkali catalyzed transesterification reaction ranges from 0.7% to 1.5% by weight, depending on the nature of oil [34]. Lower amount of catalyst results in incomplete reaction, whereas higher amount of catalyst causes soap formation. Hence, an optimum amount of catalyst is a very important parameter in the transesterification reaction. Homogeneous catalysts have few disadvantages in their application. These catalysts have to be removed from the final product with repeated washing with distilled water, which give rise to colossal generation of wastewater [38]. 5.5. Reaction temperature As a general rule, transesterification reaction is tried to be accomplished at lowest possible temperature and time [44]. The commonly employed temperature ranges from as low as room temperature to up to

65°C. Transesterification reaction has been reported to be influenced positively with increase in temperature. The boiling point of methanol is 64.7°C and hence the transesterification reaction is carried out within this range as a temperature higher than this may burn methanol. Higher temperature also favours saponification and hence must be avoided [18]. Temperature of 350°C has been considered to be optimum while using supercritical methanol [45]. 5.6. Rate and mode of stirring Scientific workers have reported stirring to be an equally important parameter for synthesis of biodiesel. Transesterification reaction was incomplete with 180 rotations per minute (rpm) of stirring, while the yield was same with 360 rpm and 600 rpm [31]. Mixing of reactants at 400 rpm with magnetic stirrer was performed by Veljkovic et al. [46] to get the optimum yield. A higher rate of stirring of 1100 rpm has also been reported to achieve maximum yield of biodiesel. Not much information on mode of stirring is available. However, a better yield with mechanical stirring has been reported than with magnetic mode of stirring [10,36]. 5.7. Purification of the final product The methyl esters obtained after one-step transesterification reaction were treated with hot water at 70°C (1/5 of methyl ester volume) and 5% H3PO4 (aq) at 50°C. After discharge of the wastewater, the ester layer was dried in vacuum and checked with ceric ammonium nitrate reagent for glycerol. Similar process was adopted for two-step transesterification method [19]. The fatty acid methyl esters were distilled by Wang et al. [47] at 180°C under vacuum (40 ± 5 mmHg) and collected. The distillation was assumed to be completed when the temperature reached 240°C (40 ± 5 mmHg) and the final yield obtained was 93.0 wt.%. Biodiesel separated after acidic transesterification was washed with petroleum ether and then with hot water (50°C) until the washing reached a neutral pH. Srivastava and Verma [30] washed the biodiesel with 10% H3PO4 by bubble wash method after separation from glycerol. Biodiesel was further purified by passing air by aquarium stone for at least 24 h. The product biodiesel is also treated by washing it with hot distilled water to remove the dissolved impurities such as catalysts, alcohol, etc. Silica gel has been reported to be used for removing the catalyst from the biodiesel product [48]. The yield of biodiesel is calculated as follows [36]:

Conversion of triglyceride to alkyl ester is calculated by titration method [40], i.e. by measurement of acid value:

PCR Amplification of 18S Rrna, Single Cell Protein Production and Fatty Acid Evaluation of Some Naturally Isolated Microalgae
Abstract Microalgae were isolated during a screening program from soil samples collected from paddy-fields of Fars province, south of Iran. The protein content was assayed by the Kochert method. Total genomic DNA were isolated and used for PCR amplification of the 18S rRNA gene. The sequences were determined for 12 species of microalgae. Some bioinformatic tools were used for more investigation on these biologic data. Total lipids from five microalgal species were extracted and used for determination of different types of fatty acids by gas chromatography–mass spectrometry method. In our experiments the green algae yielded a maximum protein of about 42% ± 1.64. The DNA

dried over anhydrous sodium sulphate and the solvent was removed by distillation under reduced pressure to give an oily substance. Esterification of fatty acids Extracted crude lipids of microalgae (0.12. and 9. salina MCCS 001 showed the most diverse strain in the studied microalgae which had 34 types of fatty acids. Furthermore D. 11. D. salina MCCS 001. The identification of FAs/FAMEs was performed through the comparison of their mass spectra with those in Wiley libraries. vulgaris MCCS 013 (Table 2) were also identified. 7-hexadecenoic acid.17-eicosatrienoic acid.15-octadecatrienoic acid (a-linolenic acid).15octadecatrienoic acid (a-linolenic acid) in C. 1990). such as chained. which is often done by saponification and esterification with methanol (Müller et al. Müller. salina MCCS 001 and the longest was octatriacontanoic acid with 38 carbon atoms in D. 6. a-linolenic acid.5. salina CCAP 19/18 (Table 4) and S. Study of Increasing Lipid Production from Fresh Water Microalgae Chlorella Vulgaris Study of increasing lipid production from fresh water microalgae Chlorella vulgaris was conducted by investigating several important factors such as the effect of CO2 concentration. Vulgaris MCCS 013 (Table 2). Scenedesmus obliquus strain 019.sequences were published in the NCBI under specific accession numbers.15octadecadienoic acid in S. myristic acid. and c-linolenic acid. 9. oleic acid. monounsaturated. Esterification of the studied microalgal fatty acids is the choice to identify those using GC/MS (Butte. palmitic acid.13-hexadecatrienoic acid. a polyunsaturated (x3) fatty acid in C.12octadecatrienoic acid (c-linolenic acid). GC/MS analysis allowed us to discover several types of fatty acids. Undecanoic acid was found in all of the studied strains but some fatty acids were found only in one strain such as 2-propenoic acid and pentanoic acid.14. vulgaris MCCS 013 (Table 2).3.10. a polyunsaturated (x6) fatty acid in D. The major fatty acids in our five studied strains of microalgae were shown to be undecanoic acid.12. different types of fatty acids are detected in the five sample strains. 10. nonanoic acid. & Nalik. 7. 1983. GC/MS analysis of fatty acids requires the conversion of fatty acids to fatty acid methyl esters.5 g) were dissolved in 3 mL of methanol in the presence of catalytic amount of sulphuric acid. and eicosanoic acid (Tables 2–6). salina MCCS 001 (Table 3). The shortest identified fatty acids was propenoic acid with 3 carbon atoms in D. 11. The obtained oily substance was injected in GC/MS for analysis.13-hexadecatrienoic acid. The drying temperature during lipid extraction from . rubescens (Table 5). palmitic acid. 3. in D. Fatty acid identification Fatty acids in the five strains of microalgae (Chlorella vulgaris MCCS 013. a monounsaturated (x9) fatty acid in S. Furthermore. 250 lm layer thickness. myristic acid.13-octadecadienoic acid and 12. alkynoic and dioic fatty acids in some naturally isolated microalgal strains and showed the presence of at least 50 fatty acids in them. the reaction mixture was washed twice with 4 mL of saturated sodium hydrogen carbonate aqueous solution.14. Scenedesmus rubescens MCCS 018) were primarily esterified and then identified through GC/MS analysis. rubescens MCCS 018 (Table 5). a polyunsaturated (x3) fatty acid in C. 2. 1990). nitrogen depletion and harvesting time as well as the method of extraction. branched.. The composition of fatty acids was mainly. The GC/MS analyses were carried out on the product of esterification (fatty acids (FAs)/fatty acid methyl esters (FAMEs)) in the above mentioned microalgae strains. The mixture was heated to reflux using Dien–Stark apparatus. After cooling. important fatty acids like oleic acid. D. 9.15-octadecadienoic acid. salina MCCS 001 (Table 3). polyunsaturated. Germany) and pure chloroform as solvent system.17-eicosatrienoic acid. Merck.10. salina CCAP 19/18.12-hexadecadienoic acid and 9-octadecenoic acid in S. Darmstadt. Then the thin-layer chromatography (TLC) was applied to monitor the progress of methyl esterification on the extracted fatty acids. a polyunsaturated (x3) fatty acid in C. The TLC was performed using silica gel 60 F254 plates (20 _ 20 cm. rubescens MCCS 018 (Table 5).9. obliquus strain 019 (Table 6). As shown in these tables (Tables 2–6). vulgaris MCCS 013 (Table 2) and 9. The total fatty acid content of each strain was about 25% of dry weight of biomass. Husamann. 7.

Effect of drying temperature Fig. Drying at very low temperature under vacuum gave the best result but drying at 60°C still retained the composition of lipid while total lipid content decreased only slightly. Since higher lipid content was obtained when the growth was very slow due to nitrogen starvation.algal biomass was found to affect not only the lipid composition but also lipid content. 2001). Lipid extraction Dry extraction procedure according to Zhu et al. was more susceptible to oxidation than saturated fatty acid. The reasonable explanation of the degradation of TG in Table 1 was the oxidation of TG at high temperature for 12 h. The ‘‘others’’ in Table 1 should therefore contained aldehydes and ketones.1. it was found that changing from normal nutrient to nitrogen depletion media will gradually change the lipid composition from free fatty acid-rich lipid to lipid mostly contained TG. The procedure was repeated three times until the entire lipid was extracted. 1.2. Oxidation of fatty acid upon exposing to high temperature has been reported (Oehrl et al. . 2. (2002) as a modification of the wet extraction method by Bligh and Dyer (1959) was used to extract the lipid in microalgal cells. The results in Table 1 in which the content of other compounds was increased seemed to confirm the previous observation. As the growth was much enhanced by increasing CO2 concentration.3. compromising between lipid content and harvesting time should be taken in order to obtain higher values of both the lipid content and lipid productivity. CO2 concentration played an important role in the increase of lipid productivity. They reported that unsaturated fatty acid. 3. Drying at higher temperature decreased the content of triacylglyceride (TG). After stirring the sample using magnetic stirrer bar for 5 h and ultrasonicated for 30 min. harvesting at the end of linear phase during normal nutrition gave the highest lipid productivity. Japan) in which two pieces of filter papers were applied twice to provide complete separation. The TG in microalgal cells obtained in the present works should consist of highly unsaturated fatty acids. The hydroperoxides formed can react further to aldehydes. However. the highest lipid productivity could be obtained during N depletion which could surpassed the productivity during normal nutrition. About 50 mL of solvents were used for every gram of dried sample in each extraction step. the samples were pulverized in a mortar and extracted using mixture of chloroform:methanol (2:1. At high CO2 concentration. ketones. cells were harvested by centrifugation at 8500 rpm for 5 min and washed once with distilled water. higher lipid content as well as higher lipid productivity may still be achieved under this condition. and fatty acids. 1 shows the effect of drying temperature on the lipid content. The solvent phase was evaporated in a rotary evaporator under vacuum at 60 8C. In addition to the increase of total lipid content in microalgal cells as a result of cultivating in nitrogen depletion media. As long as enough pulverization was applied to dried algal sample. Heating at 60°C resulted in a slight decrease of lipid content but when heating was conducted at 80°C or higher temperature. Typically. The resistance of DG after drying may indicate that they consisted of saturated fatty acids which were not easily broken down in comparison to the highly unsaturated fatty acid that may construct the TG. Bockisch (1998) and Choe and Min (2007) also reported that the degradation of TG by oxidation also resulted in the formation of hydroperoxide group (–OOH) in the chain. v/v). by reducing the incubation time of N depletion. After drying the samples using freeze drier. especially polyunsaturated free fatty acid (PUFA). the lipid content decreased significantly. ultrasonication gave no effect whether on lipid content or on extraction time. as well as the effect of drying temperature and ultrasonication time were investigated in this study. The effect of solvents having different polarities for extracting the lipid.. the samples were centrifuged at 3000 rpm for 10 min. The solid phase was separated carefully using filter paper (Advantec filter paper. At low until moderate CO2 concentration. Table 1 shows that the content of TG tend to decrease when higher temperature was applied for the drying of algal sample. no.


Bruce. Lopez. and greatly increases product separation cost. However. soap formation. increases viscosity. . Jr. acid catalysts can simultaneously catalyze both esterification and transesterification. Dora E. and James G. Soap production gives rise to the formation of gels. The fact that the homogeneous acid-catalyzed reaction is about 4000 times slower than the homogeneous base-catalyzed reaction has been one of the main reasons. David A. The alcohol as well as the catalyst must be essentially anhydrous (total water content must be 0.2 The alcohol and catalyst must also comply with rigorous specifications. Soap forms when the metal hydroxide catalyst reacts with FFAs in the feedstock (Figure 3a).SYNTHESIS OF BIODIESEL VIA ACID CATALYSIS Edgar Lotero.3 wt % or less).1-0. consequently. Yijun Liu. A simplified block flow diagram (BFD) of a typical acid-catalyzed process is shown in Figure 4 illustrating the most important steps in biodiesel production. In fact. Goodwin.3 This is required since it is assumed that the presence of water in the feedstock promotes hydrolysis of the alkyl esters to FFAs (Figure 3b) and. Kaewta Suwannakarn. acid-catalyzed transesterifications hold an important advantage with respect to base-catalyzed ones: the performance of the acid catalyst is not strongly affected by the presence of FFAs in the feedstock.

44548 Molecular formula: C18H32O2 Palmitic acid IUPAC name: hexadecanoic acid Molar mass: 256.12.478 Molecular formula: C18H36O2 Oleic acid IUPAC name: (9Z)-octadec-9-enoic acid Moalr mass: 282.cis-9.15-octadecatrienoic acid Molar mass: 278.43 Molecular formula: C18H30O2 Other names: ALA cis.12.Myristic acid IUPAC name: tetradecanoic acid Molar mass: 228.37092 Molecular formula: C14H28O2 Linoleic acid IUPAC name: all-cis-9.12.12Z.15-Octadecatrienoic acid .4614 Molecular formula: C18H34O2 Other names: (9Z)-Octadecenoic acid (Z)-Octadec-9-enoic acid cis-9-Octadecenoic acid cis-Δ9-Octadecenoic acid α-Linolenic acid IUPAC name: all-cis-9.12-octadecadienoic acid Molar mass: 280.15-Octadecatrienoic acid (9Z.cis.15Z)-9.42 Molecular formula: C16H32O2 Stearic acid IUPAC name: octadecanoic acid Molar mass: 284.–11. 2008). Chlorella vulgaris. In the three tested microalgae. Botryococcus sp.7 mg L-1 d-1 when the cells were disrupted using the microwave oven method. bead-beating. Thus.9–8. at 6. respectively.γ-Linolenic acid IUPAC name: all-cis-6. microwaves. Oleic acid was higher in Botryococcus sp.0–28. Fatty acid composition The major fatty acid composition of the tested microalgae was determined using a GC analysis (Table 2). among the tested methods.9 g L-1 when using autoclaving. sonication. were extracted using a mixture of chloroform and methanol (1:1). and 6. and Scenedesmus sp. the microwave oven method was identified as the most simple. and Scenedesmus sp. microwaves.9. The total lipids from Botryococcus sp.1–8.8–10. and a 10% NaCl solution. In a previous report (Knothe. sonication. including autoclaving. 6. Hee-Mock Oh Abstract Various methods.5304 Molecular formula: C20H40O2 Other names: n-eicosanoic acid arachic acid COMPARISON OF SEVERAL METHODS FOR EFFECTIVE LIPID EXTRACTION FROM MICROALGAE Jae-Yon Lee. bead-beating. easy. palmitic. 10.68 and 10. The lipid contents from the three species were 5. stearic.45 Molecular formula: C17H34O2 Other names: Margaric acid n-Margaric acid n-Heptadecanoic acid Heptadecylic acid n-Heptadecylic acid Arachidic acid IUPAC name: Eicosanoic acid Molar mass: 312.12-octadecatrienoic acid Molar mass: 278.75 mg g -1 .. Chi-Yong Ahn. 7.43 Molecular formula: C18H30O2 Other names: GLA Margarinic acid IUPAC name: Heptadecanoic acid Molar mass: 270.9. oleic. and a 10% NaCl solution. oleic acid (C18:1) and linoleic acid (C18:2) were commonly dominant. So-Young Jun. showed the highest oleic acid productivity at 5.1. Chan Yoo. and effective for lipid extraction from microalgae. 3. were tested to identify the most effective cell disruption method. and linolenic acid were recognized as the most common fatty acids contained in biodiesel.

18:2. 18:1. 18:0.12. nitrogen starvation. concern some other genus (Seto et al. cold filter plugging point (CFPP). 18:2. Trace amounts of 12:0 are present usually. 18:39.79 mg g -1 dw. 16:4 and 18:4 are identified. 18:1..15. In particular. 18:3 and 18:4 appear as a result of mixed culture of green algae (Murakami et al. a-18:3 is confirmed for Chlorella. are determined by the structure of its component fatty esters. 16:1. Interpreting the causes we could say that studies where 20:4 and 20:5 are rendered and no existence of 16:2 and 16:3 is found. where in addition to those found in Chlorella. viscosity. These acids can be found in almost all green algae. The productivity of oleic acid calculated based on the daily lipid productivity was highest for Botryococcus sp. bacterial contamination or impurities. dealing with different species and strains of Chlorella. 1991). Positional isomers of 16:1 and 18:1 were present often but not always. 16:0. making it the most suitable for the production of good quality biodiesel. Botryococcus sp.. as follows 14:0.dw. 1984. showed the highest oleic acid content. the above mentioned cases concern wrongly classified genus. our results coincide with those obtained by several research groups. 16:1. As such. The other. Furthermore. Results and discussion The composition of fatty acids in three species of Chlorella is presented in Table 3. Probably. among the tested microalgal species. All of them report the same qualitative composition. There are many studies of Chlorella trying to prove that it has another fatty acid composition (see Table 2). WHICH ARE FATTY ACIDS OF THE GREEN ALGA CHLORELLA? Georgi Petkov. working at very different conditions. 16:4. The properties of a biodiesel fuel. 18:0. at 5. 2008). while linoleic acid was highest in C. 1995). Our results show that Chlorella has quite a simple qualitative fatty acid composition compared to almost all green algae. oxidative stability. Fatty acids with 20 carbon atoms and four or five double bonds are considered not originating from Chlorella. Z-18:1. 16:1 and 18:1 were presented with two isomers. and outdoor in a photobioreactor. 3. by Miura et al. 16:3.7 mg L-1 d-1. Other exceptions of this composition are interpreted as mixed algal culture. Therefore. The lack of these fatty acids is rather sure chemotaxonomic marker for Chlorella. there is no study which confirms the presence of gamma-linolenic acid in Chlorella. 16:2. 2005) and decreases the CFPP for use in cold regions (Stournas et al. Here. The classification of all marine species in Table 2 as Chlorella is doubtful. Yongmanitchai and Ward. The daily lipid productivity of each microalgal species is shown in Table 1. 16:3. The three fatty acids. combustion heat. The comparison of quantitative composition at different cultivation conditions shows that the changes are relatively small. including its ignition quality. One of the isomers of 18:1 was oleic acid.. a higher oleic acid content increases the oxidative stability for longer storage (Knothe. Up to the present moment. 16:2.. namely 18:1x could be E-isomer elaidic acid or positional one (18:1). An extremely high content of gamma-linolenic acid was found in marine Chlorella sp. and lubricity. Guillermo Garcia Abstract Fatty acid composition of three species of Chlorella were studied under conditions of photoautotrophic and heterotrophic cultivation. . oils with a high oleic acid content have been reported to have a reasonable balance of fuel properties (Rashid et al. 1993. vulgaris at 19. The composition 14:0. respectively. 16:0. 1997).

hydrolysis and methylation as well as the direct transmethylation. Neyda C.. Podojil et al.. O.. Tapanes. Wright et al.. 2002). Andre´ Luis Dantas Ramos. this happens when GC analysis is performed without preliminary purification on TLC. 1986). 1986. 1980. Apart from fatty acid methyl esters. Homova et al. 1978. Wacker et al. Antunes Abstract . Unlike the fats and oils of higher plants which are predominantly acylglycerols. Aranda. P.. 17:0 and 17:1 is a firm proof that the algal culture is heavily contaminated with bacteria (DeMort et al. 1972.The presence of fatty acids with odd number of carbon atoms 15:0.. G. ACID CATALYZED HOMOGENEOUS ESTERIFICATION REACTION FOR BIODIESEL PRODUCTION FROM PALM FATTY ACIDS Donato A. Octavio Auqusto C. despite the precise extraction. the algal lipids consist of many substances so that purification of their fatty acid samples before GC is necessary. Most often. Santos. 20:1 and 20:2 can be related to impurities: not fatty acids but substances with the same retention time (Antonyan et al. Cases when native Chlorella fatty acids are accompanied by 20:0. many other substances always remain in the sample. Rafael T.

Protonation of the carboxylic moiety of the fatty acid were defined as rate determinant step for the reaction. presence of water. 45 and 60 min. Reaction conversion was estimated from the FFA content of the medium by NaOH titration.This work deals with esterification of palm fatty acids to produce biodiesel in a batch reactor.2 Esterification Reaction Reactions were performed in a stainless steel 600 mL batch reactor (PARR 4842). 10. providing an alcohol/fatty acid molar ratio (A/FA) of 3. evaluating the effect of the alcohol used. using homogeneous acid catalysts. with diglycerides and monoglycerides as intermediates. The much higher solubility of fatty acids in low chain alcohols may also be related to this observation. 11. 9. while transesterification of triglycerides consists of three stepwise reactions. maximum pressure of 10. Saponification reaction is an undesired reaction which may be promoted. Stirring velocity was kept constant (500 rpm). 15.01% w/w) is enough to promote the reaction. 16]. Samples were withdrawn at 5. type and concentration of catalysts. Reaction with methanol showed greater yields. Reaction mixture has consisted of 307 g of fatty acid mixture. The soap decreases selectivity toward biodiesel. Kinetic parameters were estimated and molecular modeling was performed.000 psi and equipped with a sample withdrawal. and the presence of glycerol.1% wt/wt) and time of reaction was considered when desired temperature (generally 130ºC) was reached. Table 1 Composition of fatty acid mixture residue 2. depending on the reaction conditions and the free acid content of the vegetable oil used. inhibits separation of the alkyl esters and glycerol and contributes to emulsion formation during the water wash [1. Methanesulfonic and sulfuric acid were the best catalysts. 3 Results and Discussion 3. especially when FFA content is higher than 1% w/w [2. stirring and heating system. Reactants were introduced together with the appropriated catalyst mass (generally 0. It was showed very clearly that the presence of water in the reaction medium showed a negative effect in the reaction velocity. with a conversion near 35% at 1 h. Figure 3 shows the effect of sulfuric acid concentration on the kinetic curves. . Esterification of FFA with low molecular weight alcoholsis another route to produce biodiesel and can be used as a pretreatment for basic transesterification reaction to convert the FFA into methyl esters and avoid saponification. This observation was assigned to the fact that alkyl esterification is a kind of one step reaction. 30. 20. 14]. 25. Increases in catalyst concentration accelerate the reaction progressively. The reaction may be represented by the following scheme: Some authors have shown that alkyl esterification of fatty acids is faster than transesterification of triglycerides [15.1 Esterification Reaction It can be observed that the reaction occurs in the absence of catalysts. 149 mL methanol or 215 mL ethanol. 12]. 10. A small amount of catalyst (0.

esterification reaction has been shifted to the left. The energy of activation for the forward reaction decreased with increasing catalyst concentration from 50745 to 44 559 J/mol. that is. but inhibition effect was also observed [25]. Martín STUDY OF THE Abstract The kinetics of the esterification of free fatty acids (FFA) in sunflower oil with methanol in the presence of sulphuric acid at concentrations of 5 and 10 wt% relative to free acids as catalyst and methanol/oleic acid mole ratios from 10:1 to 80:1 was studied. Reaction inhibition by the presence of water is commonly reported in transesterification reaction.The effect of water in the reaction medium can be seen in Fig. Based on the experimental results. J.A. soap formation is not expected. which lowers the yield of esters and renders the separation of ester and glycerol and water washing difficult. A. This is a widely endorsed limit for efficient separation of glycerin and biodiesel during production of the latter. favoring the hydrolysis of the ester. 23]. Higher inhibition of ethanol reaction may be related to phase miscibility and emulsion formation. besides favoring the hydrolysis of triglycerides and FFA [1. Inhibition effect can be observed mainly in ethanol reaction. M. which may be attributed to equilibrium constraints. Siles. In the case of acid catalyzed esterification. The experimental results were found to fit a first-order kinetic law for the forward reaction and a second-order one for the reverse reaction. A KINETIC ESTERIFICATION OF FREE FATTY ACIDS (FFA) IN SUNFLOWER OIL M. . a catalyst (sulphuric acid) concentration of 5 wt% and a temperature of 60ºC provided a final acid value for the oil lower than 1 mg KOH/g oil within 120 min. 9. Martín. 5. Berrios. The influence of temperature on the kinetic constants was determined by fitting the results to the Arrhenius equation. being attributed to the formation of soap. a methanol/oleic acid mole ratio of 60:1.

The highest rate was obtained at 60ºC. The acid value was determined as per the UNE-55001. Above 60:1. 5 and 6). an increased catalyst concentration increased the esterification rate. stearic (3%). Once a methanol/oleic acid mole ratio of 60:1 was adopted as optimal. A speed of 600 rpm was therefore subsequently used to examine the influence of the catalyst concentration. On the other hand. 2). it has been verified that the esterification reaction does not take place in catalyst absence. Materials and methods The sample contained the following major fatty acids: palmitic (6%). but required using a pressure above atmospheric level or a more sophisticated experimental set-up. methanol/fatty acid mole ratio and temperature on the acid value. a catalyst concentration of 5% provided an acid value of 4 mg KOH/g oil within 120 min. Results and discussion By means of essays. whereas one of 10% gave 2 mg KOH/g oil in the same time. In both cases. Figs. respectively. all were determined by gas chromatography in accordance with UNE-EN 14331. however. the influence of temperature at the two catalyst concentrations studied was examined. the reaction rate increased with increasing mole ratio. oleic (17%) and linoleic (72%). As expected. raising the temperature increased the esterification rate (see Figs. 3 and 4 show the variation of the acid value with the methanol/oleic acid mole ratio at a sulphuric acid concentration of 5% and 10%. 3. Thus. A higher temperature obviously increased the rate further. at a methanol/oleic acid mole ratio of 20:1.2. which is close to the boiling point of methanol at atmospheric pressure. Tests were conducted at variable agitation speeds from 200 to 600 rpm – above which this variable was found to have no further effect on the reaction rate (Fig. the increase was negligible. .

The technique of metabolic controlling through heterotrophic growth of C.864 in about 4 h of reaction time. The saponification (189. The optimum process combination was 100% catalyst quantity (based on oil weight) with 56:1 molar ratio of methanol to oil at temperature of 30°C.912 to a final value of 0.25 _m film of polyethylene glycol (VF-5ms.. Gas chromatography was performed on a 0. The GC–MSapparatus was linked to a PC running software for data acquisition and processing. flash point. The result showed that cell density significantly increased under the heterotrophic condition.d. and the highest cell concentration reached 15.0mLmin−1. and its flow rate 1. and the heterotrophic C.2×10−4 Pa s (at 40 ◦C). To increase the biomass and reduce the cost of alga. 2001).3 mg KOHg−1) and acid value (8. and heating value were measured. from VARIAN.High Quality Biodiesel Production from a Microalga Chlorella Protothecoides by Heterotrophic Growth in Fermenters Han Xu.864 kg L−1. and a viscosity of 5. cold filter plugging point.97 mg KOHg−1) of the microalgal oil were determined according to the method of Vicente et al. solidifying point. The method has great potential in the industrial production of liquid fuel from microalga. The injection temperature was 290 ◦C. viscosity.2_L) were injected in split mode (split/column flow ratio 30:1). The molecular weight of the oil was calculated from saponification and acid value as The properties of biodiesel such as density. . corn powder hydrolysate instead of glucose was used as organic carbon source in heterotrophic culture medium in fermenters. protothecoides contained the crude lipid content of 55. The composition of the biodiesel was derivatized and analyzed by gas chromatographic–mass spectrometric analysis. 1). Large amount of microalgal oil was efficiently extracted from the heterotrophic cells by using n-hexane. and then transmuted into biodiesel by acidic transesterification. 2004. Biodiesel was obtained from heterotrophic microalgal oil by acidic transesterification (Fig. rose to 300 ◦C over 20 min and was held at this temperature for 20 min (total run time 42 min). a density of 0. the oven temperature was 100 ◦C for 2 min. America). Qingyu Wu Abstract The aim of the study was to obtain high quality biodiesel production from a microalga Chlorella protothecoides through the technology of transesterification.)×30m fused silica column lined with a 0.25mm (i. Samples (0. The elemental compositions of biodiesel were determined by a CE-440 elemental analyzer (Peng et al. The column head pressure of the carrier gas (helium) was 3 kPa at the initial oven temperature.5 g L−1. protothecoides was applied.2%. which reduced product specific gravity from an initial value of 0. The biodiesel was characterized by a high heating value of 41 MJ kg−1. Xiaoling Miao.

The physical and fuel properties of bidiesel from microalgal oil in general were comparable to those of diesel fuel. beef tallow ester (BTE) and sunflower methyl ester (SME). A comparison of these properties of diesel fuel (Ma and Hanna. 2002. rapeseed methyl ester (RME). Most of the researchers/scientists reported that the production of biodiesel was more when the process was used a catalyst. cold filter plugging point. [1] followed a two-step reaction process to produce biodiesel. Antolin et al. Biodiesel is one of the best available sources to fulfill the energy demand of the world. and octadecanoic acid methyl ester are 18 carbon acid methyl esters. They concluded that vegetable oils. combustion.3. octadecadienoic acid methyl ester. More than 350 oil-bearing crops identified. linseed methyl ester (LME). Vicente et al. there is a need to find out an alternative fuel to fulfill the energy demand of the world. and heating value were determined. It was reported that the combustion characteristics of biodiesel are similar as diesel and blends were found shorter ignition delay. solidifying point. As the fossil fuels are depleting day by day. viscosity. biodiesel from microalgal oil and ASTM biodiesel standard is shown in Table 4. The gas chromatograph of biodiesel is shown in Fig. A vast majority of the scientists reported that short-term engine tests using vegetable oils as fuels were very promising but the long-term test results showed higher carbon built up and lubricating oil contamination resulting in engine failure. A Review on Biodiesel Production. higher ignition pressure and peak heat release.84%. 1999. potassium hydroxide and sodium . 2001. it observed that the base catalysts are more effective than acid catalysts and enzymes. Lang et al. The engine power output was found to be equivalent to that of diesel fuel. Using this method canola methyl ester (CME). Biodiesel produced from heterotrophic Chlorella To assess the potential of biodiesel as a substitute of diesel fuel. This study is based on the reports of about 130 scientists who published their results between 1980 and 2008.5. There were nine FAMEs derivatized in the biodiesel. Combustion. 5. 2002). higher ignition temperature. Ahn et al. 2002. flash point. Production of biodiesel Researchers and scientists had developed different methods for biodiesel production from different bio fuels. Al-Widyan and Al-Shyoukh. A brief review of these methods has presented here. In addition. performance and emissions. The fatty acid methyl esters (FAMEs) of the biodiesel are presented in Table 5. Most of these parameters comply with the limits established by ASTM related to biodiesel quality (Antolin et al. among which some only considered as potential alternative fuels for diesel engines. synthesized in a batch reactor using sodium hydroxide. 2004). and the most abundant composition was oleic acid methyl ester with the content of 60. either chemically altered or blended with diesel to prevent the engine failure. This resulted in the high quality of the biodiesel. and the total content of these three FAMEs was over 80%. The biodiesel from microalgal oil showed much lower cold filter plugging point of −11 ◦C in comparison with the diesel fuel (Table 4). the properties of biodiesel such as density. Oleic acid methyl ester. Emissions and Performance Abstract This article is a literature review on biodiesel production. The scientists and researchers conducted tests by using different oils and their blends with diesel.

[6] investigated the effects of the pretreatment of immobilized Candida antarctica lipase enzyme (Novozym 435) on methanolysis for biodiesel fuel production from soybean. using sodium hydroxide. Fatty acids . Transesterification reaction of rapeseed oil in supercritical methanol was investigated without using any catalyst by Saka and Kusdiana [9]. Waste frying oils transesterification was studied by Felizardo et al. Li et al. [3]. [27] produced biodiesel from jatropha curcas oil using a heterogeneous solid super base catalyst (calcium oxide). A two-phase membrane reactor had developed to produce biodiesel from canola oil by Dube´ et al. Issariyakul et al. Fatty acid methyl ester (FAME) production from waste activated bleaching earth discarded by the crude oil refining industry was investigated by Kojima et al. Xu et al. Meher et al. [4] presented statistical and experimental design to evaluate interdependence of process variables in enzymatic transesterification. Tashtoush et al. and potassium methoxide as catalysts. It is concluded that a trade-off between reaction time and temperature as reaction completeness is the most critical fuel quality parameter [18]. Ghadge and Raheman [23] discussed the preparation of biodiesel from high free fatty acid oils by using response surface methodology. [8]. [29] discussed the effect of fatty acid concentration and water content on the production of biodiesel. Shieh et al. The major factors affect the conversion efficiency of the process such as molar ratio. reaction temperature on quality and quantity of esters. A new enzymatic method of synthesizing methyl esters from plant oil and methanol in a solvent-free reaction system was developed by Masaru et al. Transesterification reaction of used frying oil by means of ethanol. Karmee and Chadha [22] prepared biodiesel from the Pongamia pinnata by transesterification in the presence of potassium hydroxide as catalyst. [31]. sodium methoxide. Pizarro and Park [11] studied the production of biodiesel fuel from vegetable oils contained in waste activated bleaching earth. They developed a two-step transesterification process to convert the high free fatty acid oils to its mono-esters. [25] with the purpose of achieving the best conditions for biodiesel production. [16] conducted an experimental study on evaluation and optimization of conversion of waste animal fat into biodiesel. [21] studied biodiesel production from high free fatty acid rubber seed oil. [30] had developed a new method for preparing raw material for biodiesel. [12] optimized the biodiesel production from soybean by using response surface technology. [34] optimized the whole cell-catalyzed methanolysis of soybean oil for biodiesel production using response surface methodology. Van Gerpen [18] discussed the effects of reaction time. Uosukainen et al.methoxide as catalysts. Canoira et al. Production of fatty acid methyl esters from crude tobacco seed oil (TSO) having high free fatty acids (FFA) was investigated by Veljkovic´ et al. Cvengro and Povaz [2] described biodiesel production by using two-stage lowtemperature transesterification of cold pressed rapeseed oil with methanol at temperatures up to 70°C. amount of catalyst and reaction temperature on the yield of acid-catalyzed production of methyl ester (biodiesel) from crude palm oil had been studied by Crabbe et al. [10] studied the enzymatic alcoholysis for biodiesel fuel production. Al-Zuhair et al. Royon et al. In the same year. The effect of three principal variables namely molar ratio of methanol to oil. potassium hydroxide. Zhu et al. A packed-bed reactor (PBR) system using fungus whole-cell biocatalyst has developed for biodiesel fuel production by plant oil methanolysis by Hama et al. Xue et al. [13] reported that the acid-catalyzed process using waste cooking oil has proved to be technically feasible with less complexity than the alkali-catalyzed process using waste cooking oil. In the same year. reaction temperature and reaction duration analyzed [21]. [20] had carried out transesterification of soybean oil in supercritical methanol in the absence of catalyst. [14] using fossil fuel as a solvent in the esterification of triglycerides. was studied by Encinar et al. [7] discussed the production of biodiesel using rubber seed oil. [33]. The authors also studied the alcoholysis of rapeseed oil methyl ester (biodiesel). Ramadhas et al. [32] studied the enzymatic production of biodiesel by methanolysis of cottonseed oil. Chisti [37] discussed the biodiesel production from microalgae. Cao et al. Kusdiana and Saka [15] discussed the effects of water on biodiesel fuel production by supercritical methanol treatment. [38]. Ghadge and Raheman [17] studied biodiesel production from mahua (Madhuca indica) oil having high free fatty acids. Ikwuagwu et al. Zhang et al. Fangrui and Hanna [5] had reviewed the biodiesel production. In the same year. Samukawa et al. [24] presented a process to convert the Jojoba oil wax to biodiesel by Transesterification with methanol. amount of catalyst. Yuji Shimada et al. [19] proposed a simplified model to describe the reaction kinetics of the biodiesel production. Miao and Wu[26] introduced an integrated method for the production of biodiesel from microalgal oil. [35]. [28] reviewed the technical aspects of biodiesel production by transesterification. [36] studied the production of biodiesel from waste fryer grease using mixed methanol/ethanol system.

menor punto final de ebullición y que puede contener Biodiesel. which convert the same ingredients as well as any free fatty acids to soap. leading to high yields of fatty acid methyl ester [39]. [42]. using homogeneous catalysis. The acid-catalyzed reaction also requires heat. It suffers from competing saponification reactions. que se utiliza como combustible en motores tipo diesel y que puede contener Biodiesel. acid catalyzed. BXX. Son mezclas de mono . This followed by base-catalyzed transesterification.alquil ésteres de los ácidos grasos de cadena larga derivados de aceites vegetales y grasas animales.diesel. which have high free fatty acid content.2 El biodiesel B100 debe cumplir con los requisitos indicados en la Tabla 1 del DE 100-04 (ICONTEC) Biodiesel para motores diesel.) en la mezcla final. tomando mínimo un volumen equivalente a 20 L (20 dm3). Timothy Transesterification reactions can be base-catalyzed. even free fatty acids are converted to biodiesel by esterification. or enzymatic. Es una mezcla de hidrocarburos entre 10 átomos y 28 átomos de carbono formada por fracciones combustibles proveniente de diferentes procesos de refinación del petróleo tales como destilación atmosférica y ruptura catalítica. The base-catalyzed reaction takes about one hour at room temperature. PROYECTO DE NORMA TÉCNICA COLOMBIANA NTC 1438 (Sexta actualización) 1. Mezcla de hidrocarburos similar al diesel corriente pero con un menor contenido de azufre. The first stage is acid-catalyzed esterification of the free fatty acids. DEFINICIONES 3.2 Diesel corriente. The associated acid-catalyzed esterification reaction requires only about two hours completion. There is no competing saponification reaction with the acid-catalyzed and enzymatic reactions. A combined strategy called the two-stage process can be used maximize the amount of biodiesel produced. . 4. MODELING AND SIMULATION OF REACTION KINETICS FOR BIODIESEL PRODUCTION Lawrence Turner. 3.3 Diesel extra. La letra B representa el biodiesel y XX representa su porcentaje en volumen (% vol.methyl esters had prepared by Hernando et al. REQUISITOS 4.1 Los combustibles “Diesel extra " y “Diesel corriente” deben cumplir los requisitos indicados en la Tabla 1. either in batch or in a flow system.1 Biodiesel. They reported that the process using microwaves irradiation proved to be a faster method for alcoholysis of triglycerides with methanol. In fact. menor viscosidad. 3. 3. 5. while minimizing the amount of produced. Acid-catalyzed and enzymatic transesterification require three to four days to complete. OBJETO Esta norma establece las especificaciones que deben cumplir y los métodos de ensayos que se deben usar para determinar los parámetros definidos para los combustibles utilizados en motores tipo diesel disponibles en Colombia (véase el numeral 3). Response surface methodology (RSM) based on central composite rotatable design (CCRD) was used to optimize the three important reaction variables namely methanol quantity. TOMA DE MUESTRAS Y CRITERIOS DE ACEPTACIÓN O RECHAZO 5. Son mezclas de biodiesel con diesel en diferentes proporciones. 3. 4.1 TOMA DE MUESTRAS La toma de muestras se efectúa de acuerdo con lo indicado en la NTC 1647. [39] under microwave irradiation. This approach is especially effective for waste vegetable oil and animal fats.4 Mezclas biodiesel . acid concentration and reaction time for reduction of free fatty acid content of the oil to around 1% by Tiwari et al.

Processes have been developed to produce biodiesel from high free fatty acid feedstocks. such as methanol.10-Hexadecadienoic acid IUPAC name: hexadeca-7.10-dienoic acid Molar mass: Molecular mass: C16H28O2 7. and soapstock.38 Molecular formula: C16H26O2 BIODIESEL PROCESSING AND PRODUCTION Jon Van Gerpen Abstract Biodiesel is an alternative diesel fuel that is produced from vegetable oils and animal fats. and soap. The reaction conditions generally involve a trade-off between reaction time and temperature as reaction completeness is the most critical fuel quality parameter. such as recycled restaurant grease.10. free glycerol.13-hexadecatrienoic acid IUPAC name: hexadeca-7.13-trienoic acid Molar mass: 250. or impurities in the final product. Much of the process complexity originates from contaminants in the feedstock. animal fats. .Palmitoleic acid IUPAC name: hexadec-9-enoic acid Molar mass: 254.408 Molecular formula: C16H30O2 Other names: Palmitoleic acid cis-Palmitoleic acid 9-cis-Hexadecenoic acid 7. such as water and free fatty acids.10. It consists of the monoalkyl esters formed by a catalyzed reaction of the triglycerides in the oil or fat with a simple monohydric alcohol.

the transesterification reaction is limited by the low solubility of the alcohol. While the reaction only requires 120 s. but most larger plants (>4 million liters/year) use continuous flow processes involving continuous stirred-tank reactors (CSTR) or plug flow reactors [28]. The remaining 20% of the alcohol and catalyst are added in this reactor. and while yield was reduced by 3–5% for phosphorus levels above 50 ppm. Following the reaction. The reaction is sometimes done in two steps (as suggested by the patent literature discussed earlier). Boocock proposed the addition of a cosolvent to create a single phase. which eliminates the need for the water washing step. Saka and Kusiana [30–34] claim that it is possible to react the oil and methanol without a catalyst. the purity of the final product needs to be fully characterized. this separation generally occurs quickly and may be accomplished with either a settling tank or a centrifuge. catalyst. temperatures of 300ºC – 350ºC and methanol to oil molar ratios of 42:1 are required. approximately 80% of the alcohol and catalyst is added to the oil in a first stage CSTR. However. This system provides a very complete reaction with the potential of using less alcohol than single-step systems. Dasari et al. Van Gerpen and Dvorak [20] found that phosphorus compounds in the oil did not carry over into the methyl esters. Fig. this was due mostly to added difficulty separating the glycerol from the esters.Freedman compared both crude and refined vegetable oils as feedstocks and found that the yield of methyl esters was reduced from 93% to 98% for the refined oil to 67% to 86% for the crude oil. [33] measured reaction rates without catalysts at temperatures of 120ºC to 180ºC. Then the reacted stream from this reactor goes through a glycerol removal step before entering a second CSTR. the glycerol is removed from the methyl esters. Water may be added to the reaction mixture after the transesterification is complete to improve the separation of glycerol [27. this excess methanol is usually not removed from the reaction stream until after the glycerol and methyl esters are separated due to concern about reversing the transesterification reaction. Alcohol. In a study of the effects of phospholipids on biodiesel production. especially methanol. 2 shows a schematic diagram of the processes involved in biodiesel production. and this greatly accelerates the reaction so that it reaches substantial completion in a few minutes. This was attributed mostly to the presence of up to 6. In this system. although phospholipids were also suggested as a source of catalyst destruction.35] and attributed it to catalytic effects at the surfaces of the reaction vessels and noted these effects would be exacerbated at higher temperatures. The technique is applicable for use with other alcohols and for acid-catalyzed pretreatment of high free fatty acid feed stocks.66% free fatty acids in the crude oil. They noted the difficulty of reproducing reaction kinetics results of other researchers [31. Smaller plants often use batch reactors [27]. Due to the low solubility of glycerol in the esters.29]. Boocock et al. and formation of nonmethyl ester compounds in significant amounts is possible. in the oil. The primary concerns with this method are the additional complexity of recovering and recycling the cosolvent although this can be simplified by choosing a cosolvent with a boiling point near that of the alcohol . However. [37–39] have developed a novel technique for accelerating the transesterification reaction rate. During its early stages. The excess methanol tends to act as a solubilizer and can slow the separation. and oil are combined in a reactor and agitated for approximately 1 h at 60ºC.

The salts will be removed during the water washing step. 1.7% using vacuum distillation or ion exchange processes. Then the low FFA pretreated oil can be transesterified with an alkali catalyst to convert the triglycerides to methyl esters. Some very low quality feedstocks. This water should be removed in a distillation column before the methanol is returned to the process. The free fatty acids are not soluble in the glycerol and will rise to the top where they can be removed and recycled.5% to 99. The soap that is created during the reaction is either removed with the glycerol or is washed out during the water wash.being used. as shown in the following reaction: This process can be used as a pretreatment to convert the FFAs in high FFA feedstocks to methyl esters and thereby reduce the FFA level. but additional catalyst must be added to compensate for the catalyst lost to soap. after separation from the glycerol. After acidulation and separation of the free fatty acids. After neutralization. The methanol that is removed from the methyl ester and glycerol streams will tend to collect any water that may have entered the process. When an alkali catalyst is added to these feedstocks. Methanol (77% of the weight of oil) and sulfuric acid (0. Soaps will react with the acid to form water soluble salts and free fatty acids. The salts remain with the glycerol although depending on the chemical compounds present. . The water washing step is intended to remove any remaining catalyst. the soap inhibits separation of the methyl esters and glycerol and contributes to emulsion formation during the water wash. The first step in refining the glycerol is usually to add acid to split the soaps into free fatty acids and salts. Then a molecular sieve is used to remove the water. as shown in the reaction below: Up to about 5% FFAs. Following the wash process. the glycerol has little value and disposal may be difficult. The glycerol stream leaving the separator is only about 50% glycerol. Mittelbach describes a process for esterifying these free fatty acids and then returning them to the transesterification reaction stream [40]. can be used to esterify the free fatty acids to methyl esters. tetrahydrofuran and methyl tertiary butyl ether. Keim [9] describes using this approach to convert palm oil containing 50. before water washing. soap.75% of the weight of oil) were added to the oil while stirring at 69ºC for 1 h. At this point. the methyl esters enter a neutralization step and then pass through a methanol stripper. the free fatty acids react with the catalyst to form soap and water. Special processes are required if the oil or fat contains significant amounts of free fatty acids (FFAs). which can be used for fertilizer. The methanol content requires the glycerol to be treated as hazardous waste. the glycerol should have a purity of approximately 85% and is typically sold to a glycerol refiner. The glycerol refining process takes the purity up to 99. any remaining water is removed from the biodiesel by a vacuum flash process. or free glycerol from the biodiesel. This step is more difficult if an alcohol such as ethanol or isopropanol is used that forms an azeotrope with water. and animal fats contain from 5% to 30% FFAs. Acid is added to the biodiesel to neutralize any residual catalyst and to split any soap that may have formed during the reaction. the methanol in the glycerol is removed by a vacuum flash process or another type of evaporator. usually a vacuum flash process or a falling film evaporator. an acid catalyst. such as sulfuric acid. methanol. Used cooking oils typically contain 2–7% FFAs. such as trap grease. can approach 100% FFAs. salts. the reaction can still be catalyzed with an alkali catalyst.8% free fatty acids to methyl esters. some may precipitate out. Additional concerns have been raised about the hazard level associated with the cosolvents most commonly proposed. and the free fatty acids will stay in the biodiesel. When the FFA level is above 5%. 2. In this form. One frequently touted option is to use potassium hydroxide as the reaction catalyst and phosphoric acid for neutralization so that the salt formed is potassium phosphate. Returning to Fig. It contains some of the excess methanol and most of the catalyst and soap. Neutralization before washing reduces the water required and minimizes the potential for emulsions to form when the wash water is added to the biodiesel. For these cases.25% sodium methoxide was added.

Boise.601 August. In accordance with the present invention. 2002 [27] W.560 October 3. US Patent No.164. Bioenergy 2002. Danzer. References [9] G. Process for the production of fatty acid esters of lower alcohols. Kawahara and Ono [42] propose allowing the alcohol to separate from the pretreated oil or fat following the reaction.PROCESS FOR PRODUCING LOWER ALCOHOL ESTERS OF FATTY ACIDS SUMMARY OF THE INVENTION The inventions of the present invention have therefore made intensive research to achieve a process for obtaining a high quality lower alcohol ester of a fatty acid and glycerol from an unrefined fat. 1945 [20] J. in the presence of an acid catalyst. M.H. by solving the above-mentioned defects of the conventional methods. B. Van Gerpen. September 22–26. 2. U.506 August 14. Stidham. US Patent No. with a high yield. or esterifying free fatty acids of unrefined fats with a lower alcohol in the . 1979 US PATENT 4164506 . Kawahara. Analysis showed a yield of 97% but a residual acid value equivalent to about 5% palmitic acid. Process for producing lower alcohol esters of fatty acids.and the mixture was stirred for an additional hour at 50ºC.W.I. Treating fats and fatty oils.399.S. Method for preparing a lower alkyl ester product from vegetable oil. there is provided a process for producing lower alcohol esters of fatty acids which comprises steps including: (1) esterifying free fatty acids of unrefined fats with a lower alcohol in an amount larger than the amount soluble in the fats. water is formed. Removal of this alcohol also removes the water formed by the esterification reaction and allows for a second step of esterification or proceeding directly to alkali-catalyzed transesterification. Ono. 28. ID. 4. Wimmer. The incomplete reaction was probably due to water in the reactant mixture. T. The effect of phosphorus level on the total glycerol and reaction yield of biodiesel. D.127.D. Dvorak.731 21 March 21. and if it accumulates. and thus completed the present invention. 2000 [29] T. Keim. As shown in the reaction. Patent No.F. The 10th Biennial Bioenergy Conference. Seaman.1995 [42] Y. 5. 6. [41] has described using acidic ion exchange resins in a packed bed for the pretreatment. US Patent No.383. it can stop the reaction well before completion. Jeromin et al.

the impurities such as polypeptides and phospholipids are decomposed while the fatty acid is being esterified under the acidic condition of sulfuric acid and their solubility in a lower alcohol is increased. It is different from the conventional solvent extraction method which merely removes free fatty acids by means of the solubility difference. The most characteristic feature of the process for producing lower alcohol esters of fatty acids in accordance with the present invention resides in the following points. so that the latter layer may be removed. but also simultaneously the fats are treated with an acid catalyst for the purpose of the esterification and impurities other than the free fatty acids. however. In the process of the present invention. these impurities have poor solubility in a solvent and they are hardly removed from the fat as they are. the effect of removing impurities is remarkably enhanced in the solvent extraction step. layer separation. and (3) effecting the interesterification reaction between the resulting refined fats and a lower alcohol with an alkali catalyst. (2) separating the product mixture into the fat layer and the lower alcohol layer. in the conventional solvent extraction method. After the removal of the alcohol layer separated at the end of the esterification. settling. and subjected to a layer separation procedure so as to remove the excess lower alcohol. settled. In order to restrain the interesterification reaction of the fat component. The fats and oils used as raw materials in the present invention are not refined or not completely refined. It is possible to re-use the resulting alcohol layer of this procedure in the step of adding a lower alcohol to the starting fats. The removal of these impurities is difficult without the acid treatment of the fats. it is more preferred that methanol is charged in excess at the start of the reaction and then further methanol is blown into the reaction system at the same rate as that at which methanol is being distilled out. are dissolved in the lower alcohol layer which is present in excess or is later added. and thus removed from the fats. As the result. is more preferred. it is now possible to obtain a fatty acid ester and glycerol of extremely high quality from unrefined fats and oils containing various impurities by employing the process comprising esterification. However. in order to remove water generated during the reaction. washing with lower alcohol. the solubility is from 12 to 15% by weight in the fat at 50° C. it is preferred to add methanol in an amount of 20 to 30% by weight based on the weight of the fat. layer separation and interesterification. stirring. In other words. on the other hand. and other impurities.presence of an acid catalyst and then adding the lower alcohol in an amount larger than the amount soluble in the fats. More specifically. the recovery yield of glycerol is improved because the loss caused by incorporation of the fat and the resulting emulsion is minimized. the procedure comprising adding again the lower alcohol in an amount larger than its soluble amount in the fat. in the present invention. phospholipids. may be further repeated at least once. methanol is added in an amount larger than this solubility. The solubility of an alcohol in the fat depends on various conditions. Moreover. When the cycle of these steps is repeated. the fats are improved in their quality. they contain free fatty acids. In accordance with the present invention. Accordingly. as the unreacted free fatty acid is distributed also to the lower alcohol layer to a certain extent. so it is also advantageous for the removal of the impurities. polypeptides. . not only free fatty acids in unrefined fats are esterified to reduce their acid value. a low temperature ranging from 65° to 70° C. such as polypeptides and phospholipids. The esterification of free fatty acids by the use of an acid catalyst is carried out at a temperature in the range of from 60° to 120° C. Accordingly. and the esterification method in which free fatty acids are esterified with a lower alcohol into fatty acid esters so as to reduce the acid value. After the esterification of the free fatty acid using an acid catalyst and the separation of the alcohol layer in the above-mentioned process. The esterification reaction may be carried out in a sealed system after adding a lower alcohol in excess. As to the byproduced glycerol. In the case of methanol. the lower alcohol is added to the fat in an amount larger than its soluble amount in the fat (preferably 10 to 30% by weight based on the weight the fat). According to the process of the present invention. stirred. and the resulting refined fats and the lower alcohol are subjected to the interesterification reaction using an alkali catalyst to thereby give a lower alcohol ester of the fatty acid having a further improved quality. separating and removing the alcohol layer.

a methanol blowing port and a condenser for distillates is charged with 1. the methanol layer is separated. a thermometer. 1. and atmospheric pressure and can be carried out in any given open or closed container of any given dimensions preferably provided with a discharge orifice in the bottom. The transesterification can be carried out in one or several stages. i. The acid value is lowered down to 0. Then. the transesterification is carried out in the presence of sodium hydroxide or potassium hydroxide. to +40° C.74 g of caustic soda as an alkali catalyst and 75. At 3 hours after the blowing of methanol started. and the lower glycerol layer is removed. subsequent separation and removal of the methanol layer and washing of the fat with methanol are not effected. and the mixture is stirred at 50° C.3 in this instance.or multiple-stage operation.74 g of caustic soda and 15. The reaction mixture is allowed to stand. Then 1. while 1/10 to 4/10 are added in the second stage. the stirring is also stopped and the reaction system is allowed to stand. the interesterification reaction is similarly performed between the resulting fat and methanol in the presence of the alkali catalyst to give a coconut fatty acid methyl ester and crude glycerol (pre-esterification method). Subsequent to the completed transesterification and the separation of the glycerol phase. subsequently to completed settling and separation of a glycerol phase. the amount depending on the amount of alkali or alkaline earth metal remaining in the ester phase and preferably ranging between 0. without previous separation of the glycerol phase formed in the second or last stage. The fatty acid glyceride is either transesterified with the total amount of lower alcohol and catalyst or a first stage is carried out with only a portion of the amount of lower alcohol and catalyst required for the transesterification. 0. For comparison. The esterification reaction is carried out for 3 hours at a temperature of 65° to 67° C. water can be added immediately after the second or the respective last stage.. the esterification of the fatty acid is carried out in substantially the same manner as above.000 liters.10 to 1.80 mols of a lower alcohol based on 1 mol of fatty acid bound as glyceride in the presence of an alkali or alkaline earth metal compound. The reaction mixture is again allowed to stand to separate and remove the glycerol layer.Example A four-necked flask of a 2 l-capacity equipped with a stirrer. 205 g of methanol is further added to the fat layer. The remaining amount(s) of lower alcohol and catalyst required for the transesterification are added in the same manner.6 g of methanol are added and subjected to the interesterification for about 30 minutes.PROCESS FOR THE PRODUCTION OF FATTY ACID ESTERS OF LOWER ALCOHOLS SUMMARY OF THE INVENTION It was surprisingly found that the aforementioned disadvantages can be avoided and that the requirement mentioned above can be met by carrying out the transesterification of fatty acid glycerides with 1.000 g of a raw coconut oil having an acid value of 7. US PATENT 5399731 . except that the blowing of methanol. the blowing is stopped and the reaction system is then cooled to 50° C. If the transesterification is carried out in a two-stage operation. in a second stage or in several further stages. further methanol is blown into the flask at a constant rate so as to keep the methanol in the flask in the same amount as the initially charged water and methanol. to wash the fat layer with it. Preferably. The two. .1 to 5 percent based on the ester phase of water or a diluted organic or inorganic acid are added with stirring to remove residual impurities such as in particular glycerol or catalyst residues. and withdrawing the heavy phase after it has settled. the required stirring manipulations can be carried out manually or automated if required. At batch volumes of about 2. In the same way as above.e. In two. DESCRIPTION OF THE PREFERRED EMBODIMENTS Transesterification according to the process of the present invention is preferably carried out at ambient temperatures of about +5° C.7.6 g of methanol are added to the resulting fat and subjected to the interesterification reaction at about 50° C. for about 1 hour.and multiple-stage operations entail the advantage of a further reduction of the alcohol excess. The mixture is heated. After the methanol layer is removed. There is thus obtained a coconut fatty acid methyl ester. 205 g of methanol and 1 g of 98% concentrated sulfuric acid. 6/10 to 9/10 of the total amount of lower alcohol and catalyst required are preferably added in the first stage. Thereafter. whereupon the upper methanol layer and the lower fat layer separate in a volume ratio of about 1:10.3 and 3 percent. and after methanol starts reflux.

in amounts of from 0. nitric acid. Known processes in which the removal of the catalyst residues from the ester phase is effected by one or several washing(s) with water or acids.e. of 0. Also. sulfuric acid. for instance. For instance. if the fatty acid esters are to be used as diesel fuels. the amount of transesterification catalyst remaining in the ester phase. Instead. the separation of the heavy phase can be accelerated by means of a coalescence separator. dietetic and cosmetic purposes. . the amount of catalyst used. and exceeds by up to 100 percent. for improving viscosity. In contrast to the washing operations according to the known processes. may be used so as to adapt the produced fatty acid esters to the respective intended use in a known manner. redundant for most applications. The addition of water characteristic for the present invention is not comparable to the conventional washing operations of the known processes. if necessary. rendering any further purification. for protection against oxidation. which is particularly convenient with fatty acid glycerides with sensitive highly unsaturated fatty acids such as alpha and gamma linoleic acid. for inhibiting corrosion. Any given high degree of transesterification. removal of higher melting portions of fatty acid esters by freezing. color and odor improvement or reduction of the peroxide number by treatment with bleaching earths and the like or the addition of additives such as agents for lowering the solidification point. The concentration of the acid is selected so that it is at least equivalent. eicosapenta and docosahexaenoic acids and the like because it prevents isomerizations. Instead of water.3 to 3 percent based on the ester phase. phosphoric acid could be used. can be obtained depending on the preferably cited amounts of lower alcohol and transesterification catalyst. what is involved in the present case is the hydration of the anhydrous catalyst and glycerol residues present in the fatty acid esters with the added water. The oils and fats used need not be subjected to any purification and can contain up to 20 percent and more of fatty acids in the free state in addition to slimy substances. additional drying by means of silica gel. result in great difficulties due to the formation of emulsions of fatty acids in the free state and subsequent elaborate phase separation and drying. should the intended use require it. the fatty acid esters are virtually anhydrous after the addition of water according to the invention and the settling of the heavy phase.. whereby a troublefree elimination of the catalyst residues from the ester phase and other residual impurities such as glycerol. molecular sieves.There are two substantial characterizing features of the process according to the invention. This embodiment is mainly used if very small amounts of residual catalyst are contained in the ester phase. such as it is described in the "Process for the Treatment of the Glycerol Phase Accumulating in the Transesterification of Fats and Oils with Low Alcohols" (Austrian patent application A 2357/89) of the applicant. The glycerol phase as well as the heavy phase accumulating after the addition of water which also contains glycerol and soaps. and less. In contrast. which is already evident from the small amounts of water preferably used according to the invention. no washing operations with water or acids and no ion exchangers are required for removing the catalyst residues. elimination of residual amounts of lower alcohols by means of evaporation or blowing out. can conveniently be processed with concentrated phosphoric acid. improving the cetane number and the like. The process according to the invention does not preclude that the fatty acid esters thus produced. measures such as vacuum distillation.3 to 3 percent. The operation can be carried out at low excesses of lower alcohols at ambient temperatures of +5° to +40° C. i. phosphatides and other impurities. The advantages of the process according to the invention particularly reside in the following facts. phosphatides and the like from the ester phase is made possible. Secondly. and atmospheric pressure. The transesterification can be carried out. If required. oxalic acid. the fatty acid esters can be produced in a technically extremely simple manner.1 to 5 percent. be subjected to a further purification by conventional measures. preferably of from 0. at temperatures of +5° C. whereby any given high degrees of transesterification and a trouble-free sedimentation and separation of the glycerol phase can be achieved at ambient temperature and atmospheric pressure and low alcohol excess at high degree of contamination and high content in free fatty acids in the fatty acid glycerides used. hydrochloric acid. For instance. by means of distillation. which is significant for the use of such fatty acid esters for pharmaceutical. Firstly. the addition of water or an organic or inorganic acid after transesterification. coalescence aids or the like. namely. a diluted organic or inorganic acid such as acetic acid. the process according to the invention provides for the sedimentation of the heavy phase containing the added water and the aforementioned impurities and the catalyst residues without the formation of emulsions and the ester phase can be drawn off after several hours. The glycerol phase accumulating in the process according to the invention may contain large amounts of soaps particularly when using fatty acid glycerides with high proportions of fatty acids in the free state.

D.EXAMPLE 1 A solution of 1. PROCESS DESIGN AND TECHNOLOGICAL ASSESSMENT Y. It contains less than 1.033 mols) of potassium hydroxide in 19 ml of methanol is added to 100 g of deslimed and deacidified (acid number 0.25 percent of fatty acids in the free state are charged.1. After that. the heavy phase is drained off from the bottom of the container. the glycerol phase on the bottom of the container is drained off and stirring is resumed after the addition of a solution of 6.1 kg of 100 percent KOH) in 60 l of methanol and continued for 20 minutes again. Dub_e a. The reaction was carried out with a 6:1 molar ratio of methanol to oil. Kates 4. Transesterification A continuous alkali-catalyzed process flowsheet using virgin oil was developed (Fig.461 Molecular formula: C18H34O3 Other names: R12-Hydroxy-9-cis-octadecenoic acid BIODIESEL PRODUCTION FROM WASTE COOKING OIL: 1. 60 _C and 400 . e. M. A solution of 27.or triglycerides and an ash content of 0. M. 80 kg of water are immediately added and stirring is continued for another five minutes. by sucking up in a pipette.8 kg of industrial grade potassium hydroxide (corresponding to 24. the supernatant is decanted.1. EXAMPLE 2 In a container with a cubical capacity of 2000 liters equipped with an agitator and a discharge device in the bottom. di. 0. Alkali-catalyzed process using virgin vegetable oil (process I) 4. After being left to stand for one hour. After having been left standing for 12 hours. 1% sodium hydroxide (based on oil).A. Zhang a.83 g (0.12R)-12-Hydroxyoctadec-9-enoic acid Molar mass: 298.5 percent residual fatty acid glycerides and 0. It consists of virtually pure rapeseed fatty acid methyl ester without any detectable fatty acid mono-.008 percent ash. D.07) rapeseed oil and stirred in a beaker of 250 ml cubical content by means of a magnetic agitator for 15 minutes.1. McLean.5 l of water are added and stirring is continued for 10 minutes. Ricinoleic acid IUPAC name: (9Z.. 2). After being left standing overnight. 1618 kg of unrefined rapeseed oil with a content of 2.5 kg of 100 percent KOH) in 240 l of methanol is added and stirring is continued for 20 minutes. The supernatant is suitable for use as a diesel fuel without any further treatment. After a sedimentation period of three and one-half hours.9 kg of industrial grade potassium hydroxide (corresponding to 6.g. the glycerol phase accumulated on the bottom of the beaker is drawn off.004 percent.

1. stream 305 contained 62% glycerol and was fed to T-501 to obtain 85% or 92% glycerine. Fresh methanol (stream 101 at 117 kg/h). a cooler and a pump were required to pump the unconverted oil back to the transesterification reactor.6% pure).kPa. methanol and catalyst by adding 11 kg/h water (25 _C). Stream 301A from T-301 was forwarded to T-401. FAME purification In order to obtain a final biodiesel product adhering to ASTM specifications (greater than 99. 4. Alkali removal Stream 303 (128 kg/h) was fed to neutralization reactor R-201 to remove sodium hydroxide by adding phosphoric acid (100% purity). The FAME in stream 203 was separated from the glycerol. 4. FAME distillation T-401 with four theoretical stages and a reflux ratio of 2 were used. this stream would pass to T-501 for further removal of water and methanol by distillation. A partial condenser was used to provide easy separation of the FAME from water and methanol in the column overhead. Virgin vegetable oil (stream 105) was heated in exchanger E-101 before entering R101. Consequently.g. T-401 was operated under vacuum to keep temperatures low enough to prevent degradation of the FAME.g. five theoretical stages and a reflux ratio of 2 were used to obtain a good separation between methanol and other components. 3% methanol and 9% sodium hydroxide. Water and methanol were removed in distillate stream 501. 92%) was preferred. 95% of oil was assumed to be converted to FAME. Accordingly. 4. stream 305 contained 85% glycerol. Glycerine purification After removing the sodium hydroxide.5. Unconverted oil remained at the bottom of T-401. When potassium hydroxide is used as an alkali catalyst.4. 4.6.1. The resulting Na3PO4 was removed in gravity separator X-302.. Bottom stream 202 was sent to washing column T-301 after being cooled in exchanger E-201 to 60 _C. a water washing column (T-301) with four theoretical stages was used in this study (Connemann and Fischer. . Although separation using a gravity settler was proposed by Krawczyk (1996).3. When oil conversion in reactor R-101 was low and oil recycling was necessary for waste reduction. All of the glycerol remained in the bottom stream 303 (128 kg/h). Stream 201 was a pure methanol distillate. producing glycerol as a by-product.65% purity) was obtained in stream 401 as a liquid distillate (194 _C and 10 kPa). If a glycerine by-product with a higher grade (e.1.1. Vacuum distillation was used to keep the bottom temperature under 150 _C. the size of T-401 and the energy requirement increased. fertilizer). it was treated as a waste. 4. When the UNIQUAC model rather than NRTL was employed. Since only a small amount of unconverted oil (52 kg/h) was left. Water and methanol were removed as vent gases (stream 401A). 8% water. containing 94% of the total methanol in stream 106. which contained 81% glycerol. At the bottom. the load in T-401 increased. 1998). Pure methanol (stream 1201) was mixed with fresh make-up methanol (stream 101B) and then charged back into reactor R-101.. In R-101. When the UNIQUAC model was used. Stream 106 from the reactor was introduced to methanol distillation T-201. Methanol recovery In T-201. Glycerine purification T-501 was designed with four theoretical stages and a reflux ratio of 2. methanol and catalyst. Superheated high pressure steam was the heating medium for the reboiler. The amounts of unconverted oil. the same desired purity of FAME product was obtained using either thermodynamic/activity model. the resulting potassium phosphate may be used as a valuable byproduct (e. recycled methanol (stream 1201 at 111 kg/h) and anhydrous sodium hydroxide (stream 103 at 10 kg/h) were mixed prior to being pumped into reactor R101 by pump P-101. However.2. FAME product (99.1. methanol and water in stream 301A were all less than 6%. Water washing The purpose of this step was to separate the FAME from the glycerol. a complete separation could not be achieved based on our simulation results. 92% glycerine was obtained as a high quality by-product.

a continuous alkali-catalyzed process from waste cooking oil was developed. Due to the presence of sulfuric acid. Because of their small flows. glycerine washing and methanol recovery. Acid-catalyzed process using waste cooking oil (process III) An acid-catalyzed system is insensitive to any free fatty acids in the oil. Compared to process I.94% methanol and 0. In comparison to process I. The pretreatment unit is shown in Fig. the downstream units are identical to those in process I using virgin vegetable oil.2. Transesterification .2. 1986). containing 6% free fatty acids. 3% oil. 2. stream 501 can be returned to T-301 as a washing solvent instead of fresh water. reusing these streams may be advantageous in the future. However. 7% oil and 3% water. Recovering most of the methanol in this stream for reuse in R-100 was a logical step. Once the refined oil without free fatty acids is obtained. despite the decrease in raw material cost by using waste oil. 4) appears to be a promising alternative to the alkali process. Waste treatment The compositions of streams 401A. was heated in exchanger E-100 to 60 _C before entering R-100. Glycerine washing The resulting water and acid catalyst (H2SO4) from R-100 must be removed completely before proceeding to the alkali-catalyzed transesterification. especially for larger scale processes. 1% water and traces of esters. 402 and 501 are listed in Fig. For example. these streams were treated as hazardous gas or liquid wastes.2. At 28 _C and 20 kPa. Alkali-catalyzed process using waste cooking oil (process II) To lower the cost of biodiesel. stream 106 was forwarded to glycerine washing column T-100 to remove the sulfuric acid and water.1. Recovery of the solid waste stream 306 from X-302 as a possible fertilizer credit is also feasible. these changes offer potential approaches for reducing waste treatment loads 4. process III. Stream 110A from T-100 was sent to downstream transesterification unit R-101. including esterification of the free fatty acids. 4. 2. After being cooled to 46 _C. the recycled methanol stream 1111 (188 kg/h) and the H2SO4 stream 103 (10 kg/h) were mixed before being pumped into esterification reactor R-100 by pump P-101. On the other hand. The fresh methanol stream 101 (128 kg/h). Overall.3. Esterification The esterification reaction was carried out at 70 _C. 4. stream 110B (336 kg/h) contained 60% unreacted methanol. the addition of a pretreatment unit to reduce the content of free fatty acids in the feedstock oil in process II would be expected to more than offset these savings.3. The description of process III concentrates on the differences from the previous processes I and II. 94% of the total methanol fed to the column was recovered in the distillate (i. which was realized in methanol recovery column T-101. 4. Nevertheless. 3 while the remainder of the process is identical to that shown in Fig.3. 8% methanol.4. Consequently. It contained 99. this stream was not reused and was treated as waste. 400 kPa and a 6:1 molar ratio of methanol to crude oil (Lepper and Friesenhagen. In R-100. 4. 3.2. 33% glycerol. By adding 110 kg/h of glycerine at 25 _C and 200 kPa.1. neutralizing the sulfuric acid and then recovering the glycerol is a feasible alternative to reduce waste. stream 111) at the rate of 188 kg/h.e. 3% sulfuric acid. 7% sulfuric acid. all the free fatty acids were converted to methyl esters.7. 4. Methanol recovery In T-101. was added. a pretreatment unit. The characteristics of the main streams in process II are shown in Fig.2. At 70 _C and 30 kPa..06% water and was recycled to R-100. bottom stream 112 (147 kg/h) was composed of 75% glycerol. five theoretical stages and a reflux ratio of 5 were used. The waste cooking oil stream 105A (1050 kg/h).1. all of the resulting water was removed from oil stream 110A after three theoretical stages of washing. an acid-catalyzed continuous process from waste cooking oil (Fig.

Acid removal For acid removal. glycerol and sulfuric acid from the hexane/FAME layer in stream 205A at room temperature.2. unconverted oil. FAME purification column T-401 and glycerol purification column T-501) were similar to those used for process I. component splitters T-301A and T-301B were used in simulating the hexane extraction of FAME and the methanol/water washing in process IV. 100% of the hexane and the unconverted oil.4. Acid-catalyzed process using hexane extraction (process IV) To avoid the formation of emulsions due to water washing. recycled methanol (stream 1201 at 1594 kg/h) and sulfuric acid (stream 103 at 150 kg/h) were mixed first and fed to transesterification reactor R101 by pump P-101. the use of hexane or petroleum ether as a solvent following the procedures of Nye et al. methanol. 1999). A second washing with methanol/water (T-301B) was applied to completely remove the water. 2% of the sulfuric acid and 1% of the glycerol. Two identical reactors operated in series were used. FAME. 5). a reflux ratio of 2 and vacuum distillation were employed. In reactor R-201. the results showed incomplete recovery of FAME in hexane. instead of a liquid–liquid extraction unit. 1999). In methanol distillation column T-201.4. Based on amounts of these components in feed streams 203 and 205. the reaction conditions were set to a 50:1 molar ratio of methanol to oil. 4% of the methanol and the water. In R. To decrease hexane solubility. glycerol. was employed to remove the CaSO4. in our current simulations CaSO4 rather than CaSO4_2H2O was considered as a solid waste. The following discussion pertains to the units downstream of methanol distillation column T-201. In terms of equipment sizing and operating conditions. the reaction mixture contained methanol.3. 97% of the oil was assumed to be converted to FAME after 4 h. 8% methanol. 4. Calcium oxide was used primarily due to its low-cost relative to other alkali substances. The operating conditions for the units from reactor R-101 to methanol distillation T-201 were the same as those in process III. After T-201. sulfuric acid. Detailed descriptions of these separations follow.3:1 molar ratio of sulfuric acid to waste oil. Also the water produced would be absorbed by the resulting CaSO4 to form CaSO4_2H2O. methanol recovery was the first step following the reaction in order to reduce the load in the downstream units. The lower layer (stream 205B) consisted of the remaining glycerol.3. five theoretical stages.e. 4. 99.On the basis of discussions in Section 2. 4.101. Hexane extraction . a 1. X-201.5% of the FAME. sulfuric acid was completely removed in a neutralization reaction by adding calcium oxide (CaO) to produce CaSO4 and H2O. When hexane was added and a liquid–liquid extraction was used in simulating hexane extraction of FAME. sulfuric acid and water. As in process I. the design principle was the same as for alkali removal in process I. resulting a clear-cut separation of hexane/FAME and methanol/water phases (McBride. Fresh methanol (stream 101 at 216 kg/h).. the remaining water washing column (T-301) and purification units (i. 4. indicated as R-101A/B in Fig. Methanol recovery Because of the large excess of methanol in stream 106. This was due partly to the lack of information in the HYSYS on interaction parameters in such a complex multi-component system and also to the fact that hexane is soluble in anhydrous methanol. However.3. 9% glycerol. water was added to the methanol in the ratio 1:10 by volume. were in the upper layer (stream 205A) from T-301A. a 94% methanol recovery rate was achieved in stream 201 and recycled to R-101. Bottom stream 202 was forwarded to acid removal unit R-201. Waste cooking oil (stream 105 at 1030 kg/h) entered R-101 after being heated to 60 _C in exchanger E-101. since absorption of water by CaSO4 is relatively slow. A gravity separator. 2% unconverted oil and 2% water proceeded to water washing column T-301. to separate the FAME from other components was proposed in process IV (Fig.1. a reaction temperature of 80 _C and a pressure of 400 kPa. we assumed that a good separation between the FAME/hexane and glycerol/methanol/water phases was achieved after the addition of hexane and water. 4. On the basis of our experimental results (McBride. The resulting stream 203C (1247 kg/h) consisting of 79% FAME. (1983) and McBride (1999). In addition.2.

4%). It was then passed to the downstream FAME distillation column T-401 to remove the hexane. 0. Transesterification reactions were performed in a 1-L three-necked flask equipped with a reflux condenser. Antonio Bula e Homero Sanjuán El reactor se cargó con 500ml de aceite y se sumergió en baño de temperatura constante hasta alcanzar la temperatura deseada. Glycerine purification Stream 303A entered T-501 for a five-theoretical stage distillation and a reflux ratio of 2. a thermometer. A known amount of potassium hydroxide (the catalyst) was dissolved in the required amount of methanol and heated separately to the desired temperature. depending on the desired degree of purity. ratio of water to methanol was 1:10) were added to T-301A at 25 _C and 200 kPa. At various times. After hexane extraction in T-301A. T-401 was principally used for distilling the hexane from the FAME. Darnoko and Munir Cheryan Batch reaction.2 μ m poly tetra fluoroethylene syringe filter and kept at -20/C until further analysis. The main components of bottom stream 205B were methanol (27%).3. they entered R-201 for sulfuric acid removal by adding calcium oxide. and a sampling port. an equal volume of hexane (0. Distillate stream 401 was the FAME product (99. glycerol (28%).2° C.13 m3/h) and 0. In T-301B. 4. Separate studies had determined that this dilution and neutralization stopped the reaction immediately. KINETICS OF PALM OIL TRANSESTERIFICATION IN A BATCH REACTOR D. 4. The sample was then filtered through 0. About 300 mg of the sample mixture was placed in a vial and diluted with 5 mL high-performance liquid chromatography grade tetrahydrofuran. The reactor was immersed in a constanttemperature water bath equipped with a temperature controller. Initially. Glycerine with 85% or 92% purity.4.Based on the methanol volume in stream 203. neither glycerol nor sulfuric acid remained in the FAME and hexane stream 301A. After T-301B.65%) and stream 402 from the bottom of T-401 contained any unconverted oil. could be obtained in stream 502 by different energy requirements.2.14 m3/h methanol–water (80:20 v/v) was added.6 N hydrochloric acid was added to neutralize the catalyst. the reactor was filled with 500 g palm oil and heated to the desired temperature. stream 205A was forwarded to a second washing unit (T-301B) at 25 _C and 150 kPa.01 m3/h water (vol. which was set at a constant speed throughout the experiment. and then one drop of 0. CINÉTICA DA TRANSESTERIFICAÇÃO DA OLEÍNA DE PALMA AFRICANA COM ETANOL Adrián Ávila. as in process III.4. At a total flow rate of 492 kg/h. At five theoretical stages and a reflux ratio of 3. Agitation was provided with a magnetic stirrer. that was capable of maintaining the temperature within ± 0. FAME purification Because most of the methanol remained in the glycerol stream after the hexane extraction and second methanol/water washing. vent gases (stream 401A) were discharged from the top of T401 and recycled to T-301A to reduce the need for fresh solvent (stream 110). The weight of 1 mol oil was determined from the calculated average molecular weight of palm oil based on the known fatty acid composition of the oil. Stream 205B from T301A was combined with stream 301B from T-301B. A portion of top stream 501 (112 kg/h) was returned to T-301B as the solvent for the second washing. This methanolic KOH was then added to the base of the reactor (to prevent evaporation of methanol) at which point the reaction was assumed to have started. sulfuric acid (40%) and FAME (1. Por separado se preparó etóxido (solución de etanol con KOH) y se calentó . a sample was withdrawn quickly from the reactor with a Pasteur pipet. The molar ratio of methanol/oil was fixed at 6:1 since the literature suggests that this is the optimal ratio for vegetable oil transesterification.

SG is fluid specific gravity. . 1. 20. it was around 2.833. A sealed 2. Da is turbine diameter (mm). NRe was referred to the start of the reaction. 3. Type R2R1 (Heidolph. cuya función es neutralizar el catalizador y por tanto evitar la continuación de la reacción. 1. and sampling port was used in this study. con una frecuencia mayor durante el comienzo de la reacción. 20. las muestras se pasaron a través de unos filtros de membrana de 0. Los productos obtenidos en la reacción de transesterificación difieren de manera considerable en sus características físicas y reactividad química. hexane. Model EYELA SB-24 & T-80 (Tokyo Rikakikai Co. it was capable of controlling the temperature to within ±0. and benzene used in the analysis were all of pro analysis grade. Charktir Tongurai and Michael Allen 2 . 1. n is turbine speed (rpm). Japan). una acuosa donde residen las sales formadas por el ácido y el catalizador.45μm y se almacenaron para su posterior análisis. Las curvas de calibración se hicieron utilizando estándares para los etil ésteres. integrador. 50 y 100min. El flujo utilizado para la fase móvil fue de 1ml·min-1. digital thermometer.1 Materials A refined palm oil. a los 0. con una frecuencia mayor durante el comienzo de la reacción. Se utilizó un cromatógrafo Lachrom-HITACHI Mod : L-7100.000 mL glass reactor equipped with a mechanical stirrer. where NRe is Reynolds number. The mixing intensity is presented by Reynolds number (NRe) of impeller in Eq. Después de una extensa búsqueda se encontró que el método más adecuado. De esta última capa de cada una de las muestras se tomaron 100μl y se diluyeron en 10ml de 2-propanol. por lo cual se dificultó conseguir un método adecuado para realizar un método único de análisis para las muestras tomadas. Chloroform. a los 0. (1) [11]. cuya función es neutralizar Se tomaron muestras a diferentes intervalos de tiempo durante el transcurso de la reacción (120min). Se tomaron muestras a diferentes intervalos de tiempo durante el transcurso de la reacción (120min). se adicionó al reactor y se comenzó a medir el tiempo transcurrido. Gumpon Prateepchaikul. En total se tomaron nueve muestras. En los tubos de ensayo se formaban dos capas. 35. Germanny).Ltd. The free acid content of the oil was determined according to AOCS official method Ca 5a-40 [10] to be 0. formic acid. A SECOND ORDER KINETICS OF PALM OIL TRANSESTERIFICATION Theerayut Leevijit. mono-di y triglicéridos. samples were withdrawn with a 2 mL pipettes through the sampling port. 2 . 1. A mechanical stirrer. Para detener la reacción se utilizaron tubos de ensayo de 10ml que contenían 4ml de HCl 1N.000. Una vez diluidas.2 Apparatus The experimental set up is shown in Fig. and μ is fluid dynamics viscosity (Pa. de acuerdo a los recursos disponibles y la viabilidad técnica. 1. provisto de un detector UV. During the reaction. fitted with a stainless steel 6-blade disk turbine provided the sufficient mixing. Worawut Wisutmethangoon. y otra capa donde están los productos y subproductos de interés.5.1 °C.5.833. 3.64 %. The reactor was immersed in a constant-temperature circulating water bath.s).. era la cromatografía líquida de alta resolución (HPLC). 35.hasta llevarlo a la temperatura del aceite. 5. En total se tomaron nueve muestras. a commercial methanol of 95 % purity. 5. diethyl ether. 50 y 100min. Para detener la reacción se utilizaron tubos de ensayo de 10ml que contenían 4ml de HCl 1N. y una columna ZORBAX XDB C18. and a commercial sodium hydroxide pellets were used in this study.

THE EFFECT OF WATER ON THE TRANSESTERIFICATION KINETICS OF COTTON SEED OIL WITH ETHANOL Elena Bikou. Argiro Louloudi. 2 . TG. The reactor assembly was then placed in the circulation water bath and heated to the designed temperature.2 .5 Analysis The samples were analyzed by thin layer chromatography/flame ionization detector (TLC/FID) [12. air flow rate 2. The ester phase was then centrifuged to ensure a thorough separation. The ester phase was kept at –20 °C until further analysis. ME. Separate studies had determined that these procedures stopped the reaction immediately. The samples were diluted in chloroform and 1 μL of the solution was spotted on each rod. At each time of neutralization and washing. The mixture was then suddenly washed twice with distilled water: first 8 mL of distilled water was added to the test tube and the mixture was washed in 300 mL flask filled with 200 mL of distilled water. Then the ester phase and water phase formed separate liquid layers. The mechanical stirrer was started as soon as possible. glycerol. A measured amount of methanol and sodium hydroxide solution was heated separately to the reaction temperature and added to the reactor.3 Procedures The reactor was initially charged with 650 g of refined palm oil. more frequent sampling was required. Analyses were performed using an Itronscan MK-6 with Chromarod type S-III quartz rod (Mitshubishi Kagaku Iatron Inc.4 Sampling Samples of about 2 mL were withdrawn at pre-specified time intervals.0 L/min. and Nikos Papayannakos 2 Experimental 2. Approximately 17 samples were collected during the reaction (90 min). speed 30 s/scan.13]. DG. and MG were effective separated. The rods were developed in hexane/diethyl ether/formic acid (50:20:30 vol/vol/vol) for 8 cm and hexane/benzene (1:1 vol/vol) for 10 cm. a vigorous mixing was provided by the mixer. At the beginning of the reaction. The reaction was timed when the solution was added. Japan). 2 . methanol and remaining sodium hydroxide or sulfuric acid were transferred to the water phase.6 N sulfuric acid to neutralize the catalyst. The weight percentages (%wt) of the reaction compositions on a glycerol-free basis were determined.. Upon washing.1 Materials . Each sample was collected in 20 mL test tube filled with 6 drops of 0. peak areas were calculated with chromatography data system ChromStar. The rods were dried and scanned under the following conditions: hydrogen flow rate 160 mL/min.

2 ± 0. 30. 60. ACP Chemicals Inc. It was used directly without further treatment.-% (by weight of oil) potassium hydroxide. preheated to 70 1C and fed into the reactor by a liquid pump. 6:1 and 9:1 ethanol/oil molar ratio and 99.4% mole ethanol) from Riedel de Haen and ii) “96% extra pure” ethanol (87. (St. oleifera). MO). Sam’s University Tavern. Experiments were carried out at 4:1.2 2. diolein. derived from rapeseed oil (Brassica napus ssp. 2.2. Standard triolein. The upper phase was purified with deionized water at a ratio of water/sample at least 3:1 vol/vol. methyl oleate.6%and 87. Each mixture in turn was transferred to the reactor. glycerol and sulfuric acid by partitioning between hexane and methanol–water (10:1 v/v).-%. 12% of diglyceride (DG). 78. Dube. care was taken to gently agitate the samples while washing. The temperature of the reactor was controlled and maintained at 70 or 80 1C by means of LabViewTM software. All oil samples were freed from methanol. two phases were revealed: the upper transparent yellow oily phase consisting of the ethyl esters. equipped with an internal cooling coil. glycerin and minor contaminants (< 1±2 wt. which was then sealed and pressurized. sampling port and a reflux condenser using cold tap water to condense methanol vapor (to prevent buildup of excessive pressure).150 kg refined cottonseed oil and the appropriate quantity of ethanol-water mixture were added to a 500 ml three-necked flask equipped with a mechanical stirrer (vertical propeller. Since the ethyl esters have an extremely high tendency to form an emulsion on contact with water. BDH Chemicals Inc. 10.2.5 wt. The mechanical stirrer was started.1.A.2. M. were used as catalyst in all cases. Experimental procedures 2. 98.D.2 _C in all cases. oleic acid and glycerol were obtained from SigmaAldrich Co. the mixture was heated to the reaction temperature (70 or 80 1C). 120 and 180 min reaction time and they were quickly quenched to stop reaction with cold (T = 2±4 _C ) deionized water.5–42.5% mole ethanol) from Merck Co. Kates. Analytical grade potassium hydroxide pellets from Mallinckrodt Co.2 Transesterification Reaction Procedure 0. Louis. Samples (3 ml each) were withdrawn at 2. was added rapidly and timing of the reaction began.0 and 95. The mixture was stirred and heated up to boiling point. 2.2.6% mole pure ethanol were prepared by properly mixing two types of commercial ethanol: i) “absolute” ethanol (99.Taken into account only the fatty acids with a content higher than 0.5 psia) at 80 1C. and the lower water phase of white emulsion consisting of water.0%. 95. 1 wt. and cooled to room temperature. and thereafter at 30 min intervals. ACID-CATALYZED PRODUCTION OF BIODIESEL FROM WASTE FRYING OIL S. The residual catalyst and the nonreacted excess of ethanol were distributed between the two phases.-%). for 3 times. its molecular weight is calculated equal to 860 [8]. 90.5 psia) at 70 1C and 266–293 kPa (38. a variable speed two-blade propeller turbine agitator. The appropriate amount of oil (see Table 1) was separately measured out.5%mole ethanol in the mixture ethanol-water. D. thermometer and condenser. 82% triglyceride (TG) and little or no detectable monoglyceride (MG). McLean 2.4%. Ethanol-water mixtures with 98. Procedure Methanol (reagent grade. monoolein. M. free of erucic acid) contained 6% by weight of free fatty acid (FFA). The waste oil (canola oil.5–27. then the catalyst. After being centrifuged. Heating was continued for 3 hours. and the condenser cooling water was turned on. The reaction was timed from when the oil was all pumped in (usually o1 min). Ottawa) were used in the experiments. concentrated sulfuric acid (ACS grade. the intermediates diglyceride and monoglyceride and the nonreacted triglyceride. Apparatus The apparatus used for the transesterification reaction was a 5-L stainless-steel jacketed reactor.) and waste frying oil (from a local restaurant. Methanol and sulfuric acid were premixed in the mole ratios given in Table 1. Zheng. The reaction was allowed to proceed for 4 h or more. maximum speed 1500 rpm). Five milliliter samples were collected at 5 min intervals for the first 30 min. 5. 20.). Pressure was allowed to vary from 169 to 190 kPa (24. as described .

Da is the impeller diameter. Refined and bleached soybean oils were obtained from Archer Daniels Midland Company (Lincoln. All reactions were carried out at atmospheric pressure. 6200.20 wt% sodium hydroxide in soybean oil. which was heated separately to the reaction temperature.3 g). 40. Measured amount of the methanol/sodium hydroxide stock solution (44. an initial delay in the reaction was experienced. it is referring to the start of the reaction.2% purity were purchased from Fisher Scientific Company (Pittsburgh. Noureddini and D. and sample collection was delayed accordingly.400 for rotational speed of 150. PA) which was capable of controlling the temperature to within ± 0. respectively [9. respectively. KINETICS OF TRANSESTERIFICATION OF SOYBEAN OIL H. In the following sections when the mixing intensity is presented by NRe. Fisher Scientific (Fairlawn. The rotational speed of the impeller was set at 150. NJ) fitted with a stainless steel folding propeller provided the mixing requirements. Sampling and analysis. During the course of the experiment. A mechanical stirrer Model SL 1200. Three different mixing intensities were used to investigate the effect of mixing on the kinetic behavior. Samples were drawn at pre-specified time intervals. was added to the reactor and the mechanical stirrer was started. and 600. and triolein and methyl oleate.and 2- . samples were withdrawn with a 2-mL disposable pipette through an opening on top of the reactor. The intermediate and final products (MG. di-. where n is the rotational speed of the impeller. was used in all experiments. A 6:1 molar ratio of this stock solution with soybean oil amounted to about 0. which is a typical ratio for Transesterification of vegetable oils. A 0. The reaction was timed as soon as the mechanical stirrer was turned on. Experiments were designed to determine the reaction rate constants. Approximately 15 samples were collected during the course of each reaction (90 min). The numerical values for NRe at the beginning of the reactions were determined to be 3100. The reactor assembly was then placed in the circulating constant-temperature bath and heated to the desired temperature. (McGraw Park.9% purity was purchased from Baxter Diagnostics Inc. and 600 rpm. The reactor was initially charged with 200 g of soybean oil. built-in condensing coil. which is primarily due to lower viscosity of the products.elsewhere [9]. The frequency of sample collection varied and was dictated by the reaction conditions. PA). TG.10]. and 12. A 6:1 molar ratio of alcohol to soybean oil. Procedures. This phenomenon is explained in later sections. Zhu Materials. using calibration curves generated for pure standards of mono-. the resulting oil was analyzed offline by GPC [9] for the oil to FAME conversion. and sample port was used in all kinetic experiments. The mixing intensity may also be presented by Reynolds number (NRe). Reactions at higher temperatures and mixing intensities required more frequent sampling at the beginning of the reaction. Model 1157 VWR Scientific (Philadelphia. Samples were taken at 1. and 70°C were studied. and FAME) in the oil samples were also analyzed quantitatively by GPC. Reaction conditions. Sodium hydroxide pellets of 98. As the reaction temperature and mixing intensity were decreased.907 wt% stock solution of sodium hydroxide in methanol was prepared and used in all of the reactions. Apparatus.09%. DG. To examine the temperature dependency of the reaction rate constants. A 1500-mL glass cylindrical reactor equipped with a mechanical stirrer. 300. 300. 60. Certified methyl alcohol of 99. The hexane phase was separated and brought to dryness in vacuo in a rotary evaporator. Louis. respectively. reactions at 30. IL). and ρ and μ are the fluid density and viscosity. Free acid content of the oil was determined according to AOCS method #Ca 5a-40 (15) to be 0. NE). 50. The impeller rotational speed and the NRe are related in Equation 1.01°C of the set point. The high-performance liquid chromatography (HPLC) standards for methyl esters were obtained from Sigma Chemical Company (St. There is a significant increase in NRe values as the reaction progresses. The reactor was immersed in a constant-temperature circulating bath. thermometer. MO).

DE) Chemstation Software. Melek Tuter. The transesterification reaction scheme is shown in Figure 2.min intervals. there are many components in the product mixture. Riviera Beach. Data collection and analysis were performed with Hewlett-Packard (Wilmington. glycerol (GL) and sodium hydroxide are transferred to the water phase. Upon washing. Figure 3 shows the scheme of the hot water washing method. A Spherisorb OSD 2 column (Phase Separation Inc. The crude ester phase was washed with hot distilled water at a 1:1 ratio in the following order: (1) two times without stirring (washings 1 and 2) and (2) three times with stirring (washings 3-5). The refining yield decreased with increasing temperature. Refining Method of Washing with Hot Distilled Water. The refining yield was calculated by dividing the amount of the pure ester product by the amount of the rapeseed oil used in the transesterification reaction. all the integration results were corrected for the weight percentage of the individual components. This method was applied by washing the mixture with distilled water at three different temperatures (50. The three different methods used were (1) washing with hot distilled water. and the column temperature was set at 35° 15-min intervals. Lincoln.70 mL/min. .6 mm with 80 Å pore size and 5 μm particle size) was used for the separation. IV (Thermal Separation Products. acid value. CT) (250 × 4. All of the results are given as the average of the repeated experiment results. and esters and unreacted GL form a separate liquid layer. and (3) neutralization with sulfuric acid (1:1). early in the reaction. acid values. The layers were then centrifuged at 1600 rpm for about 15 min to ensure a thorough separation. The catalyst was separated in solid state in the reaction vessel. NE). Separation of the ester and glycerin phases was performed by letting them stand for 5 h in the separatory funnel. the water amount. Norwalk. Samples were collected in 10-mL test tubes filled with 4 mL of distilled water. acid value. The test tubes were kept in an ice bath at about 5°C prior to use. and ME composition of the ester product were found to be very similar. 65.. and TG were used to establish the calibration charts. K. 80 °C). Samples (2 mL) were quenched in the test tubes by placing them in the ice bath immediately after removal from the reactor. Standards for methyl esters. later in the reaction. First the ester product and then glycerin and byproducts must be obtained from this mixture. Barıs Cıgızoglu. INVESTIGATION OF THE REFINING STEP OF BIODIESEL PRODUCTION Filiz Karaosmanoglu. As can be seen. Using these calibration charts. After completion of the reaction. The water contents. and composition of biodiesel at three different working temperatures are given in Table 3. The HPLC pump operated at 0. was used for the analysis. At all three temperatures. The test tubes were then shaken to stop the reaction. FL). MG. equipped with a model 2350 pump and a refractive index detector. The refining yields and the results of the analysis for the determination of the water content. Refracto Monitor. and composition of the biodiesel obtained in these three different methods were investigated. and at 10. Another operation was not applied to washing waters. The mobile system was degassed for 15 min in an ultrasonic bath before use in the HPLC system. Temperature for the column was controlled with a circulating constanttemperature bath. DG. The HPLC mobile phase consisted of a 50:50 volumetric mixture of acetone and acetonitrile. An HPLC (ISCO. the mixture was cooled to room temperature and transferred to a separatory funnel by decantation. The ester phase was left over the heated Na2SO4 (25% of the amount of the ester product) overnight and then filtered. and Serap Ertekin Investigation of the Biodiesel Refining. (2) dissolving in petroleum ether and then washing with distilled water.

the pH of the solution was adjusted to 7 by adding acetic acid. the mixture was cooled to room temperature and then transferred to a separatory funnel by decantation. The washing process with distilled water was repeated three times. Methanol was removed in a rotary evaporator while water of the ester product was removed by leaving the product over the heated Na2SO4 . Refining Method of Neutralization with Sulfuric Acid (1:1). The results obtained with this method are shown in Table 4. Following the separation of ester and glycerin layers. the methanol in the ester phase was removed in a rotary evaporator under vacuum. With the same principle. Sulfuric acid (1:1) was added until a neutral pH was obtained. The ester phase was separated by centrifugation from the salt formed by the addition of the acid. this method has been applied in two different ways by using solid catalyst and the solution of solid catalyst in methanol. After completion of the transesterification reaction. The petroleum ether was removed in the rotary evaporator under vacuum.92. The aim of using the solution of NaOH in methanol was the reobtainment of the catalyst as a salt resulting from neutralization with H2SO4. The ester phase was left over the heated Na2SO4 (25% of the amount of the ester product) overnight and then filtered. The scheme of this method is shown in Figure 4. The catalyst was separated in solid form in the reaction vessel. In this method. the catalyst was removed by decantation from the product mixture and the product mixture was transferred to a separatory funnel for separation of the ester and glycerin phases The pH of the ester phase was found to be 11.Refining Method of Washing with Water and Petroleum Ether. The ester phase was then taken again to the separatory funnel. (a) Use of Catalyst in Solid Form. After the addition of petroleum ether (equal to the ester phase volume) and distilled water (at 20 °C and equal to twice the ester phase volume). similar to the two previous methods.

(25% of the amount of the ester product) overnight. At the end of the reaction. The mixture was neutralized by adding H2SO4 (1:1) solution. and the results are given in Table 6. . (b) Use of Catalyst Dissolved in Methanol. The scheme of this method is shown in Figure 6. the pH was found to be 13.6% by weight of the oil) was dissolved in methanol and added to the reaction flask after heating to 68 °C. and the results are given in Table 5. leading to separation of the glycerin and ester phases.07. The methanol in the ester phase was removed by a rotary evaporator. After the removal of the salt (Na2SO4) formed by centrifugation. The scheme of this method is shown in Figure 5. the reaction was performed at 65 °C. the ester phase was transferred to a separatory funnel. while the glycerin phase was removed by washing three times with distilled water (at 20 °C). The necessary amount of catalyst for the transesterification reaction (1. The water in the ester product was removed by leaving the product over the heated Na2SO4 (25% of the amount of the ester product) overnight and was then removed by filtration.

Sign up to vote on this title
UsefulNot useful