ARTICLE pubs.acs.org/IECR
Exoskeleton of a Mollusk (Pila globosa) As a Heterogeneous Catalyst for Synthesis of Biodiesel Using Used Frying Oil Shweta Agrawal, Bhaskar Singh, and Yogesh Chandra Sharma* Department of Applied Chemistry, Institute of Technology Banaras Hindu University, Varanasi 221 005, India ABSTRACT: A heterogeneous catalyst has been derived from a waste material (i.e., exoskeleton of mollusk) for transesterification of a waste feedstock (i.e., used frying oil (UFO)) for synthesis of biodiesel. The exoskeleton of mollusk shell was crushed, ground, and calcined at 900 °C to derive CaO as a heterogeneous catalyst. The catalyst was characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray fluorescence spectroscopy (XRF), and differential thermal analysis/thermogravimetric (DT/TG) analysis. The XRD peaks observed at 2θ = 31.80, 36.93, and 53.37° were characteristic of CaO and showed high crystallinity. The FTIR absorption bands of the calcined shell were observed at 1474, 870, and 502 cm1, which are attributed to the vibration of CO32 molecules, and a sharp peak at 3640 cm1 indicated the presence of OH stretching due to Ca(OH)2. The XRF analysis demonstrated the Pila globosa shell to comprise 79.86% of calcium along with few minor elements (viz. Pd, I, Te, Sb, Sn, W, Al, Si, Sr, Cr, S). The (DT/TG) analysis showed the decomposition of calcium carbonate present in Pila globosa at 860 °C. The waste-driven substances (exoskeleton of mollusk as catalyst and UFO as feedstock) resulted in a high yield (92%) and conversion (97.8%) of biodiesel that was obtained at a 10:1 (methanol to oil) molar ratio, 4.0 wt % catalyst, at 60 ( 0.5 °C in 5 h reaction. The conversion of UFO to biodiesel was determined by 1H FT-NMR.
1. INTRODUCTION Biodiesel refers to fuel produced from renewable sources that meets widely accepted specifications (e.g., ASTM D 6751).1,2 Biodiesel is manufactured from a variety of plant oils (edible and nonedible), waste cooking oils (e.g., yellow grease), or animal fats (e.g., beef tallow).3 The advantages of usage of biodiesel as transport fuel are its high energy return, displacement of petroleum fuel, and reduction of greenhouse gas emissions.4 Biodiesel has the potential to eliminate as much as 90% of air toxins such as particulate matter, hydrocarbons, carbon monoxide, and sulfur dioxide.5,6 Biodiesel (fatty acid alkyl esters) is synthesized using oils or fats with an alcohol in the presence of a catalyst. A useful byproduct, i.e., glycerol, is also formed. The fatty acid alkyl esters is termed as biodiesel and the byproduct (glycerol) is separated. The catalyst used in the synthesis process of biodiesel is either homogeneous, or heterogeneous (including immobilized enzymes).79 Alkali catalysts are commonly used in synthesis of biodiesel due to their faster rate of reaction and lesser corrosiveness to the equipment used in their production.10 However, heterogeneous catalysts have been explored recently due to their easy separation from the product and reusability. The commonly employed homogeneous catalysts include NaOH, KOH, and CH3ONa. The heterogeneous group of catalysts constitutes a wide range including CaO, MgO, hydrotalcite, TiO2 grafted on silica, and vanadyl phosphate.11 Sakai et al.7 used KOH as homogeneous catalyst and CaO as heterogeneous catalyst for comparison of their economical prospects in production of biodiesel. The biodiesels obtained from both the catalysts were purified by either hot water (W) or vacuum distillation (D) and it was observed that CaO with hot water purification process resulted in lowest manufacturing cost among the two catalysts with the two modes of purification (KOH-W, KOH-D, CaO-W, CaO-D). Sun et al.8 reports that basicity and activity of the catalyst are correlated. The stronger basicity r 2011 American Chemical Society
of the catalyst resulted in higher yield of biodiesel. Xie et al.12 loaded ZnO with lithium by impregnation method to obtain a solid base catalyst for transesterification of soybean oil and obtained a conversion of 96.3% in 3 h, 12:1 methanol to oil molar ratio at the reflux of methanol. Sotoft et al.9 used enzymes as catalyst for preparation of biodiesel. However, it was observed that the enzymes contributed a major portion toward the cost of biodiesel. Among the feedstock, the cost ranges were 50% for enzymes, 47% for oil, and 3% for methanol. A lower group alcohol (preferably methanol) is usually preferred for transesterification due to faster rate of reaction.13 Biodiesel can also be synthesized by using supercritical methanol without using a catalyst, though the process is cost intensive.14,15 The use of homogeneous catalyst (NaOH, KOH, and CH3ONa) poses the problem of its removal from the product.16 As the catalysts are highly basic, a stoichiometric amount of acid is required for its neutralization. Also, water is required for the washing of the crude biodiesel and consequently a subsequent amount of wastewater is generated. The yield of biodiesel also decreases on repeated washing and a large amount of dehydrating agent is needed to remove water from biodiesel. To overcome these problems, heterogeneous catalysts have gained popularity as they could be regenerated, reused, and make the purification of crude biodiesel simpler.17 Recently, biodiesel has been utilized as an alternative fuel for fishing boats in Taiwan and found that 20% substitution of mineral diesel with biodiesel will be costeffective in accordance with emission reduction.18 The feedstock Special Issue: Alternative Energy Systems Received: October 19, 2011 Accepted: November 27, 2011 Revised: November 24, 2011 Published: November 27, 2011 11875
dx.doi.org/10.1021/ie202404r | Ind. Eng. Chem. Res. 2012, 51, 11875–11880
Industrial & Engineering Chemistry Research contributes toward the major cost in the production of biodiesel, which amounts to 7585% of the total production cost.19 Hence, cheaper alternative feedstocks have been explored in recent times to produce biofuel that could be economically competitive with the prevailing petroleum-based fuel.20 The heterogeneous catalysts that have been employed by researchers include Na/NaOH/γ-Al2O3, alum, ion-exchange resin, and SnCl2.2124 The synthesis of these catalysts involves several steps that takes longer time and are mostly cost intensive. Hence, utilization of a waste material as a catalyst can be of immense importance in synthesis of biodiesel to reduce the cost of biodiesel production. To utilize the waste materials as catalyst, researchers have recently derived CaO from various waste materials viz. chicken egg shell, waste mud crab shell, and mollusk.2527 The feedstock that can be used for food should be avoided as raw material for preparation of biodiesel.28 The use of waste cooking oil as feedstock can reduce the production cost of biodiesel to a significant extent as it is available at a lower price.29 The cost of waste frying oil amounts to about half the price of virgin oil.30 Waste cooking and frying oil is generated in huge quantities in many countries and, at times, they may even be procured without any cost.31,32 A waste material, Pila globosa also called “Apple Snail”, which is used in experimental work at colleges and discarded after experimentation, has been used as a raw material for the synthesis of a heterogeneous catalyst. The global availability of Pila globosa is not known. However, the genus Pila is native to both Africa and Asia.33 The Pila globosa shells and the fresh organisms are used in ayurvedic medicines and eaten as well in India, China, and other nations.34 The life cycle of Pila globosa is less than three months and they are reproductive throughout the year.33 In India, the snail shell is used for dissection purpose in zoology laboratories. In the present work, the mollusk shell, i.e., exoskeleton of Pila globosa has been used for preparation of a heterogeneous catalyst for transesterification of used frying oil (UFO) to bring down the production cost of biodiesel.
2. MATERIALS AND METHODS 2.1. Materials. The UFO was obtained from a local restaurant at Varanasi, India. The virgin oil of UFO was soybean (refined) oil. The mollusk (Pila globosa) shell was procured from a zoology laboratory of Agrasen PG College, Varanasi, India. Methanol of AR grade was obtained from Fischer Scientific Mumbai, India and ortho-phosphoric acid (H3PO4) of AR grade was procured from Merck, Mumbai, India. 2.2. Characterization of UFO. The UFO was filtered by Whatman filter paper (no. 42) to remove the suspended particles present in the discarded oil. After filtration, the UFO was dried in a hot air oven for 2 h at 105 °C to remove the moisture. The acid value of the oil was determined by titration with KOH as per ASTM D 6751 test method. The fatty acid composition of the UFO was obtained by FT-NMR spectrometer using deutrated chloroform (CDCl3) as solvent.35 2.3. Catalyst Preparation and Characterization. The DTA/ TGA of waste shell of Pila globosa was conducted with Structured Text Analyzer (DTA/TGA) model STA 409 Metzsch Geratebau GMBH (Germany) under nitrogen flow at pressure of 1.5 bar and flow rate of 2 L/h. The rate of increment of temperature was 10 °C per minute. Based on the decomposition temperature of calcium carbonate (i.e., 860 °C), the crushed Pila globosa shell was calcined at 900 °C for 2.5 h in a tubular muffle furnace. Calcination was also done at varying temperatures to observe the
ARTICLE
effect of calcination on the catalytic activity. The structural and microstructural characterization of the dry powder of calcined Pila globosa shell (i.e., CaO) was done by X-ray diffraction (Rigaku DMAX III B with CuKα radiation). The functional groups present in the catalyst were obtained from Varian 1000 FTIR instrument. The pellets of the catalyst were made by taking 1:50 ratio of catalyst to KBr. The FTIR spectra were recorded in the range of 4000 400 cm1. The calcined catalyst was also characterized by X-ray fluorescence in ARL OPTIM’X X-ray analyzer (Thermo scientific). 2.4. Transesterification Process. The transesterification of UFO was carried out by taking 100 mL of oil and 40 mL of methanol (10:1 molar ratio) with 4.0 wt % of catalyst at a constant temperature and constant agitation speed. The entire content was placed in a 3-necked round-bottom flask fitted with a mechanical stirrer in the middle neck and a thermometer in the side neck. The UFO was initially heated to 60 °C. A fixed amount of freshly prepared 4 wt % catalystmethanol solution (with respect to oil) was added to the oil. It was taken as the starting time of the reaction. The heating and stirring were terminated after 5 h and the reaction was quenched by applying ice on the outer surface of the round-bottom flask. The products of the reaction were allowed to settle overnight producing three distinct phases (i.e., methyl ester on top, glycerol in the middle, and catalyst at the bottom). After separation of the methyl ester from the glycerol and catalyst phase, 1.0 mL of H3PO4 was added to neutralize the product. H3PO4 has been used for neutralization instead of HCl, H2SO4, and HNO3 because of the nontoxic nature of H3PO4. Also, H3PO4 is a weaker acid as compared to the other acids and hence will cause less corrosiveness. 2.5. Analysis of Fatty Acid Methyl Esters (Biodiesel) Conversion and Yield. The conversion of UFO to methyl esters was analyzed by using FT-NMR. The area under the signals of methylene and methoxy protons have been used to monitor the yield of transesterification.35 Knothe and Kenar36 have derived an equation for the determination of biodiesel (eq 1). The disappearance of signal at 4.3 δ and appearance of a sharp peak at 3.663 δ indicates the formation of FAME. 2AME ð1Þ C ¼ 100 3ACH2 C denotes the conversion (%) of triglycerides to fatty acid methyl esters; AME is the integration value of the protons of methyl esters, and ACH2 is the integration value of the methylene protons. The factors 2 and 3 in numerator and denominator are attributed to the number of protons (2) on methylene and number of protons (3) on methyl ester. The yield was calculated using eq 2 given by Leung and Guo.16 Product Yield ð%Þ ¼ weight of product=weight of raw oil 100
ð2Þ The error calculated in the measurement of yield of biodiesel amounted to (1.0%.
3. RESULTS AND DISCUSSION 3.1. Characterization of the UFO. The density of the UFO was determined and was found to be 0.9118 kg/L. The viscosity of UFO was determined to be 39.52 cSt at 40 °C. The FT-NMR spectra of UFO were determined. Quaterlet peaks that were characteristic of the triglycerides were observed at 4.1 and 4.3, respectively. The proportions of oleic (O), linoleic (L), linolenic 11876
dx.doi.org/10.1021/ie202404r |Ind. Eng. Chem. Res. 2012, 51, 11875–11880
Industrial & Engineering Chemistry Research
ARTICLE
Table 1. Composition of Fatty Acid Acyl Group fatty acid acyl groups
UFO (%)
linolenic acid (C 18:3)
0
linoleic acid (C 18:2)
44.0
oleic acid (C 18:1)
29.9
saturated fatty acid
25.0
free fatty acid total
0.84 99.74
(Ln), and saturated acyl groups (S) were evaluated using eqs 36.37 Ln ð%Þ ¼ 100½B=ðA þ BÞ
ð3Þ
L ð%Þ ¼ 100½ðE=DÞ 2ðB=A þ BÞ
ð4Þ
O ð%Þ ¼ 100½ðC=2DÞ ðE=DÞ þ ðB=A þ BÞ
ð5Þ
S ð%Þ ¼ 100½1 ðC=2DÞ
ð6Þ
The proportions for the different acyl groups present have been depicted in Table 1. The UFO comprises mainly linoleic acid (44.0%), followed by oleic acid (29.9%), whereas, linolenic acid has been found to be absent. The molecular weight of the UFO was determined to be 925.49 g/mol as per the equation given by Komers et al.38 3.2. Characterization of the Catalyst. The Pila globosa shells were cleaned with tap water and then with double distilled water. It is a hard structured shell and was crushed in an agate mortar. DT/TG Analysis. The decomposition temperature of calcium carbonate present in the Pila globosa shell was determined by differential thermal and thermogravimetric (DT/TG) analysis. A 23.0 mg sample of uncalcined mollusk shell was taken for differential thermal and thermogravimetric analysis. Figure 1a depicts the decomposition temperature of crushed shell of Pila globosa. The weight loss observed from TGA occurred from 380 to 860 °C. This indicates the decomposition of CaCO3 present in the shell initiated at 380 °C. The complete decomposition (accounting for weight loss of 40.48%) was observed at 860 °C. The conversion obtained upon calcination of Pila globosa at 800 °C was only 11% which indicates that 800 °C is not adequate for formation of CaO phase. At 860 °C, calcium carbonate completely decomposed to calcium oxide and carbon dioxide (Figure 1a). XRD Analysis. The XRD spectra of the calcined catalyst were obtained with Cu Kα radiation (λ = 0.15406 nm) at 40 kV, 30 mA at a scan speed of 1.0°/min and a scan range of 2080°. The XRD spectra obtained were compared with the Joint Committee on Powder Diffraction Standards (JCPDS) file. The sharp spectra obtained were an indication of high crystallinity of the catalyst obtained after calcination. (Figure 1b). The peaks that are characteristic of CaO were observed at 2θ = 31.80, 36.93, and 53.37°. Similar peaks at 32.3, 37.4, 53.9° characteristic of CaO were also observed by Sharma et al.39 when chicken eggshell was calcined to obtain heterogeneous catalyst. The occurrence of minor peaks at 2θ = 63.5 and 67.5 show presence of some other compounds present in the calcined Pila globosa shell in minor amount. Sharma et al.39 observed peaks of Ca(OH)2 at 2θ = 14.7, and 17.8 upon calcination of eggshell. However, no peaks of Ca(OH)2 was observed in the calcined Pila globosa shell which may be due to the fact that the diffraction pattern was taken from 2θ = 20° onward.
Figure 1. Catalyst characterization: (a) DTA/TGA of uncalcined mollusk shell; (b) XRD of the calcined catalyst at 900 °C; (c) FTIR of the calcined catalyst at 900 °C. 11877
dx.doi.org/10.1021/ie202404r |Ind. Eng. Chem. Res. 2012, 51, 11875–11880
Industrial & Engineering Chemistry Research
Figure 2. FT NMR spectrum of biodiesel obtained from Pila globosa shell catalyst concentration 4 wt %, 8:1 molar ratio of methanol to oil, 5 h stirring.
FTIR. The FTIR spectra of Pila globosa shell obtained after calcination at 900 °C is depicted in Figure 1c. The spectrum was taken at room temperature. The absorption bands of the calcined shell occurred at 1474, 870, and 502 cm1 which can be attributed to the vibration of CO32 molecules. Whereas vibration at 1474 cm1 occurred due to asymmetric stretch, vibrations at 870 and 502 cm1 occurred due to out-of plane bend and inplane bend for CO32 molecules, respectively. A sharp peak at 3640 cm1 indicates the presence of OH stretching band which indicates presence of Ca(OH)2 which must have formed from exposure of CaO to atmospheric air. Similar peaks of calcined catalyst at 1470, 820, and 3625 cm1 were obtained by Sharma et al.39 XRF Analysis. The XRF analysis was carried out on calcined Pila globosa shell at 900 °C for 2.5 h to determine its chemical composition. It was found that calcium is the major element present in the Pila globosa shell which comprised 79.86% of the total composition. The elements after calcination of catalyst include calcium in majority (79.86%) followed by palladium (7.09%), iodine (2.26%), tellurium (2.02%), antimony (1.61%), tin (1.33%), tungsten (1.06%), aluminum (0.594%), silicon (0.554%), strontium (0.549), chromium (0.326%), and sulfur (0.041%). The rest of the unidentified elements together comprised 2.704%). Viriya-empikul et al.,27 however, report calcium to constitute 99.0% of the total constituent of the golden apple snail shell along with silicon (0.4%), sulfur (0.3%), and strontium (0.2%) as minor constituents. 3.3. Estimation of the Percentage Conversion of UFO to Esters by FT-NMR. The conversion of biodiesel from Pila globosa shell was obtained to be 97.8% in 5 h. The FT-NMR spectrum of biodiesel obtained is depicted in Figure 2. The experiments was done using phase transfer catalyst (tetramethyl ammonium iodide). Because methanol and oil are insoluble in each other, the quaternary ammonium salt is useful in intermixing of these two phases. However, in the present study, the conversion increased from 97.8 to 98.11% on use of tetramethyl ammonium iodide and thus its application appears to be insignificant. Therefore, the phase transfer catalyst was not taken in the present study. Also, the phase transfer catalyst will increase the production cost of biodiesel synthesis. The single factor experiments of the
ARTICLE
variables such as catalyst concentration, reaction temperature, methanol to oil molar ratio, and agitation intensity were optimized to obtain a high yield and conversion of biodiesel. 3.4. Effect of Catalyst Concentration on Yield. The effect of catalyst obtained from Pila globosa shell on the transesterification of the UFO was investigated by varying its concentration from 0.5 to 5.0 wt % (based on the molecular weight of UFO). The reaction was carried out at 60 °C for 5 h and 10:1 methanol to oil ratio (i.e., 40 mL methanol in 100 mL of oil). When the catalyst concentration was increased from 4.0 to 4.5 wt %, the yield of the biodiesel product dropped from 97.78% to 96.0% (Figure 3a). The maximum yield is obtained at 4.0 wt % CaO obtained from the calcination of the Pila globosa shell. This amount is higher than the amount of catalyst (calcined egg shell) used by Sharma et al.39 However, this amount is quite less than that used by Nakatani et al.40 where 25 wt % of the catalyst (calcined oyster shell as a source of CaO) was found to be optimum. 3.5. Effect of Reaction Temperature. The temperature of the reaction was varied from 40 to 70 °C with catalyst concentration of 4.0 wt %. The yield of biodiesel gradually increased by increasing the temperature from 40 to 60 °C. A high yield of 97.80% was obtained at 60 °C. Thereafter, a decrease in the yield was observed when the temperature was increased to 70 °C. Methanol has a boiling point quite below this temperature, and its loss may have resulted in lowered yield at this temperature. Hence, 60 °C was the optimum temperature for a conversion and yield of biodiesel (Figure 3b). This value is near that used by Sharma et al.31 where 65 ( 5 °C was found to be optimum for a high yield of biodiesel. 3.6. Effect of Methanol to Oil Ratio. The methanol/oil ratio is also an important factor affecting the yield of biodiesel. The effect of the methanol/oil ratio on the yield of biodiesel at a temperature of 60 °C in the presence of 4.0 wt % calcined CaO catalyst was studied. The amount of the methanol was varied from 20 to 50 mL per 100 mL of oil with 4.0 wt % catalyst amount at 60 °C. The maximum yield was obtained at 40:100 mL ratio of methanol to oil (Figure 3c). Various researchers have adopted methanol to oil molar ratio for optimization of methanol amount for transesterification. Viriya-empikul et al.27 observed 12:1 to be optimum for the transesterification and Sharma et al.39 found 10:1 methanol to oil molar ratio to be optimum for synthesis of biodiesel. 3.7. Effect of Agitation Speed. The vegetable oil is immiscible with methanol. Hence, to overcome the mass transfer limitation, oil and methanol are brought in contact via agitation. Common modes of agitation that can be adopted are magnetic and mechanical agitations. In this study, a mechanical stirrer was used. The stirring rate of mechanical stirrer used in the present study was varied from 500 to 1200 rpm. A much lower yield of biodiesel at 500 rpm was observed, which increased on increase in rate of agitation. The optimum yield was found to be at 1100 rpm. Beyond this, no further increase in the yield was observed. A small decrease (almost the same that was obtained at 1100 rpm) in the yield of biodiesel was obtained at 1200 rpm and that is insignificant. At an agitation speed lower than 1100 rpm, sufficient contact could not be established, resulting in a much lowered yield (Figure 3d). The catalyst, Pila globosa shell, fits well as a potential source of heterogeneous catalyst with high activity after calcination at 900 °C. A high yield (92%) and conversion (97.8%) of biodiesel were obtained at a moderate methanol to oil molar ratio (i.e., 10:1), 4.0 wt % catalyst at 60 ( 5 °C in 5 h, and is comparable with the findings of other authors. Sharma et al.40 also obtained a high yield and conversion of 95.0% and 97.4%, respectively, using chicken eggshell (calcined at 900 °C) as catalyst and 11878
dx.doi.org/10.1021/ie202404r |Ind. Eng. Chem. Res. 2012, 51, 11875–11880
Industrial & Engineering Chemistry Research
ARTICLE
Figure 3. (a) Effect of catalyst concentration on yield (%) of used frying oil methyl esters. [methanol to oil ratio, 8:1; temperature, 60 °C; agitation speed, 1100 rpm; reaction time, 5 h]. (b) Effect of temperature on yield (%) of used frying oil methyl ester [methanol to oil ratio, 8:1; catalyst amount, 4.0 wt %; agitation speed, 1100 rpm; reaction time, 5 h]. (c) Effect of methanol ratio to oil on yield (%) of used frying oil methyl ester [catalyst amount, 4.0 wt %; agitation speed, 1100 rpm; reaction temperature, 60 °C; reaction time, 5 h]. (d) Effect of agitation speed on yield (%) of used frying oil methyl ester [methanol to oil ratio, 8:1; catalyst amount, 4.0 wt %; reaction temperature, 60 °C; reaction time, 5 h].
Pongamia pinnata as feedstock at a comparatively lower methanol to oil molar ratio (i.e., 8:1), catalyst amount (2.5 wt %), and time (2.5 h) at 65 ( 5 °C. Wei et al.25 calcined the eggshell at 1000 °C to form CaO as catalyst and obtained 95% yield of biodiesel at 9:1 methanol to oil molar ratio, 3 wt % of catalyst at 65 °C in 3 h. Boey et al.26 reported the optimum conditions for transesterification using Scylla serrata shell as catalyst calcined at 700 °C (to derive CaO) to be methanol to oil mass ratio of 0.5:1, catalyst amount of 0.5 wt % at 65 °C, with the agitation rate of 500 rpm to obtain a high conversion (>99%) of biodiesel. Viriya-empikul et al.27 found the catalytic activity of golden apple snail (Pila globosa) shell to be comparable with that of eggshell upon calcination at 800 °C obtaining a high yield (>95%) of biodiesel though a comparatively higher catalyst amount (10 wt %) and methanol to oil molar ratio (12:1) at 60 °C.
4. CONCLUSIONS CaO is a very widely used catalyst for biodiesel synthesis, but most of these catalysts are of commercial grade. The exoskeleton of mollusk (Pila globosa) was calcined at 900 °C for 2.5 h for the conversion of CaCO3 to CaO. The CaO obtained was utilized as
a heterogeneous catalyst for synthesis of biodiesel from UFO. The usage of waste products both as catalyst and feedstock bears economic as well as environmental significance. The cost of biodiesel synthesis is reduced and a sustainable environment is maintained. The conversion of feedstock to biodiesel was found to be 97.8% using 4.0 wt % of catalyst with 10:1 molar ratio of methanol to oil. The international European Nation (EN) norm with a minimum value of 96.5% has also been fulfilled.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected]. Tele.: +91 542 6702865. Fax: +91 542 2368428.
’ ACKNOWLEDGMENT S.A. is thankful to UGC for grant of Junior Research Fellowship. ’ REFERENCES (1) Ma, F.; Hanna, M. A. Biodiesel production: A review. Bioresour. Technol. 1999, 70, 1. 11879
dx.doi.org/10.1021/ie202404r |Ind. Eng. Chem. Res. 2012, 51, 11875–11880
Industrial & Engineering Chemistry Research (2) Stamenkovic, O. S.; Velickovic, A. V.; Veljkovic, V. B. The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives. Fuel 2011, 90, 3141. (3) Sharma, Y. C.; Singh, B. Development of biodiesel: Current Scenario. Renew. Sust. Energ Rev. 2009, 13, 1646. (4) Bakeas, E.; Karavalakis, G.; Fontaras, G.; Stournas, S. An experimental study on the impact of biodiesel origin on the regulated and PAH emissions from a Euro 4 light-duty vehicle. Fuel 2011, 90, 3200. (5) Maceiras, R.; Vega, M.; Costa, C.; Ramos, P.; Marquez, M. C. Effect of methanol content on enzymatic production of biodiesel from waste frying oil. Bioresour. Technol. 2009, 88, 2130. (6) Csernica, S. N.; Hsu, J. T. Reverse-Phase Ternary Phase Diagram, Tie Lines, and Plait Point for Commercial Biodiesel-Glycerol-Methanol. Ind. Eng. Chem. Res. 2011, 50, 1012. (7) Sakai, T.; Kawashima, T.; Koshikawa, T. Economic assessment of batch biodiesel production processes using homogeneous and heterogeneous alkali catalysts. Bioresour. Technol. 2009, 100, 3268. (8) Sun, H.; Ding, Y.; Duan, J.; Zhang, Q.; Wang, Z.; Lou, H.; Zheng, X. Transesterification of sunflower oil to biodiesel on ZrO2 supported La2O3 catalyst. Bioresour. Technol. 2010, 101, 953. (9) Sotoft, L. F.; Rong, B. G.; Christensen, K. V.; Norddahl, B. Process simulation and economical evaluation of enzymatic biodiesel production plant. Bioresour. Technol. 2010, 101, 5266. (10) Chang, A. F.; Liu, Y. A. Integrated Process Modeling and Product Design of Biodiesel Manufacturing. Ind. Eng. Chem. Res. 2010, 49, 1197. (11) Serio, M. D.; Cozzolino, M.; Giordano, M.; Tesser, R.; Patrono, P.; Santacesaria, E. From Homogeneous to Heterogeneous Catalysts in Biodiesel Production. Ind. Eng. Chem. Res. 2007, 46, 6379. (12) Xie, W.; Yang, Z.; Chun, H. Catalytic Properties of LithiumDoped ZnO Catalysts Used for Biodiesel Preparations. Ind. Eng. Chem. Res. 2007, 46, 7942. (13) Pinto, L. F.; da Silva, D. I. S.; da Silva, F. R.; Ramos, L. P.; Ndiaye, P. M.; Corazza, M. L. Phase equilibrium data and thermodynamic modeling of the system (CO2 + biodiesel + methanol) at high pressures. J. Chem. Thermodyn. 2012, 44, 57. (14) Sawangkeaw, R.; Bunyakiat, K.; Ngamprasertsith Continuous production of biodiesel with supercritical methanol: Optimization of a scale-up plug flow reactor by response surface methodology. Fuel Process. Technol. 2011, 92, 2285. (15) Hawash, S.; Kamal, N.; Zaher, F.; Kenawi, O.; Diwauri, G. E. Biodiesel fuel from Jatropha oil via non-catalytic supercritical methanol transesterification. Fuel 2009, 88, 579. (16) Leung, D. Y. C.; Guo, Y. Transesterification of neat and used frying oil: Optimization for biodiesel production. Fuel Process. Technol. 2006, 87, 883. (17) Omar, W. N. N. W.; Amin, N. A. S. Biodiesel production from waste cooking oil over alkaline modified zirconia catalyst. Fuel Process. Technol. 2011, 92, 2397. (18) Lin, C. Y.; Huang, T. H. Costbenefit evaluation of using biodiesel as an alternative fuel for fishing boats in Taiwan. Mar. Pollut. 2012, 36, 103. (19) Siddiquee, M. N.; Rohani, S. Experimental analysis of lipid extraction and biodiesel production from wastewater sludge. Fuel Process. Technol. 2011, 92, 2241. (20) Randazzo, M. L.; Sodre, J. R. Cold start and fuel consumption of a vehicle fuelled with blends of diesel oilsoybean biodieselethanol. Fuel 2011, 90, 3291. (21) Kim, H. J.; Kang, B. S.; Kim, M. J.; Park, Y. M.; Kim, D. K.; Lee, J. S.; Lee, K. Y. Transesterification of vegetable oil to biodiesel using heterogeneous base catalyst. Catal. Today 2009, 9395, 315. (22) Aderemi, B. O.; Hameed, B. H. Alum as a heterogeneous catalyst for the transesterification of palm oil. Appl. Catal., A 2009, 370, 54. (23) Kitakawa, N. S.; Honda, H.; Kuribayashi, H.; Toda, T.; Fukumura, T.; Yonemoto, T. Biodiesel production using anionic ion exchange resin as heterogeneous catalyst. Bioresour. Technol. 2007, 98, 416.
ARTICLE
(24) Cardoso, A. L.; Neves, S. C. G.; da Silva., M. J. Kinetic study of alcoholysis of the fatty acids catalyzed by tin chloride (II): An alternative catalyst for biodiesel production. Energy Fuels 2009, 23, 1718. (25) Wei, Z.; Xu, C.; Li, B. Application of waste egg shell as low cost solid catalyst for biodiesel production. Bioresour. Technol. 2009, 100, 2883. (26) Boey, P. L.; Maniam, G. P.; Hamid, S. A. Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst. Bioresour. Technol. 2009, 100, 6362. (27) Viriya-empikul, N.; Krasae, P.; Puttasawat, B.; Yoosuk, B.; Chollacoop, N.; Faungnawakij, K. Waste shells of mollusk and egg as biodiesel production catalysts. Bioresour. Technol. 2010, 101, 3765. (28) Camara, L. D. T.; Aranda, D. A. G. Reaction Kinetic Study of Biodiesel Production from Fatty Acids Esterification with Ethanol. Ind. Eng. Chem. Res. 2011, 50, 2544. (29) Bezergianni, S.; Dimitriadis, A.; Kalogianni, A.; Knudsen, K. G. Toward Hydrotreating of Waste Cooking Oil for Biodiesel Production. Effect of Pressure, H2/Oil Ratio, and Liquid Hourly Space Velocity. Ind. Eng. Chem. Res. 2011, 50, 3874. (30) Encinar, J. M.; Gonzalez, J. F.; Reinares, A. R. Biodiesel from Used Frying Oil. Variables Affecting the Yields and Characteristics of the Biodiesel. Ind. Eng. Chem. Res. 2005, 44, 5491. (31) Patil, P. D.; Gude, V. G.; Deng, S. Biodiesel Production from Jatropha Curcas, Waste Cooking, and Camelina Sativa Oils. Ind. Eng. Chem. Res. 2009, 48, 10850. (32) Kulkarni, M. G.; Dalai, A. K. Waste Cooking Oils An Economical Source for Biodiesel: A Review. Ind. Eng. Chem. Res. 2006, 45, 2901. (33) www.applesnail.net. (34) Prasuna, C. P. L.; Narasimhulu, K. V.; Gopal, N. O.; Rao, J. L.; Rao, T. V. R. K. The microstructures of biomineralized surfaces: A spectroscopic study on the exoskeletons of fresh water (Apple) snail, Pila globosa. Spectrochim. Acta A 2004, 60, 2305. (35) Gelbard, G.; Bres, O.; Vargas, R. M.; Vielfaure, F.; Schuchardt, U. F. 1H nuclear magnetic resonance determination of the yield of the transesterification of rapeseed oil with methanol. J. Am. Oil Chem. Soc. 1995, 72, 1239. (36) Knothe, G.; Kenar, A. G. Determination of fatty acid profile by 1 H NMR spectroscopy. Euro. J. Lipid Sci. Technol. 2004, 106, 88. (37) Guillen, M. D.; Ruiz, A. Rapid Simultaneous Determination of Proton NMR of Unsaturation and Composition of Acyl Groups in Vegetable Oils,. Eur. J. Lipid Sci. Technol. 2003, 105, 688. (38) Komers, K.; Stloukal, R.; Machek, J.; Skopal, F. Biodiesel from rapeseed oil, methanol and KOH3. Analysis of composition of actual reaction mixture. Euro. J. Lipid Sci. Technol. 2001, 103, 363. (39) Sharma, Y. C.; Singh, B.; Korstad, J. Application of an Efficient Nonconventional Heterogeneous catalyst for Biodiesel synthesis from Pongamia pinnata oil. Energy Fuels 2010, 24, 3223. (40) Nakatani, N.; Takamori, H.; Takeda, K.; Sakugawa, H. Transesterification of soybean oil using combusted oyster shell waste as a catalyst. Bioresour. Technol. 2009, 100, 1510.
11880
dx.doi.org/10.1021/ie202404r |Ind. Eng. Chem. Res. 2012, 51, 11875–11880
