Bioresource Technology 101 (2010) 37653767

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Waste shells of mollusk and egg as biodiesel production catalysts

N. Viriya-empikul a, P. Krasae b, B. Puttasawat b, B. Yoosuk b, N. Chollacoop b, K. Faungnawakij a,*
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), 111 Thailand Science Park, Phahonyothin Rd., Klong Luang, Pathumthani 12120, Thailand b National Metal and Materials Technology Center (MTEC), National Science and Technology Development Agency, 114 Thailand Science Park, Phahonyothin Rd., Klong Laung, Pathumthani 12120, Thailand
a

a r t i c l e

i n f o

a b s t r a c t
The solid oxide catalysts derived from waste shells of egg, golden apple snail, and meretrix venus were employed to produce biodiesel from transesterication of palm olein oil. The shell materials were calcined in air at 800 C with optimum time of 24 h to transform calcium species in the shells into active CaO catalysts. All catalysts showed the high biodiesel production activity over 90% fatty acid methyl ester (FAME) in 2 h, whilst the eggshell-derived catalyst showed comparable activity to the one derived from commercial CaCO3. The catalytic activity was in accordance with the surface area of and the Ca content in the catalysts. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 28 September 2009 Received in revised form 17 December 2009 Accepted 18 December 2009 Available online 15 January 2010 Keywords: Biodiesel Heterogeneous catalyst Waste shells of mollusk and egg CaO

1. Introduction Recently, alternative energies, for example, H2 energy (Faungnawakij et al., 2008), solar energy (Bach et al., 1998), and biodiesel (Pinto et al., 2005; Nakatani et al., 2009), have been focused worldwide because of recent energy crisis. Biodiesel is one of the interesting alternative fuels which can be produced from renewable sources (Helwani et al., 2009). The conventional process of biodiesel production proceeds in transesterication of oils or fats using homogeneous catalysts. However, the homogeneous catalytic process suffers some drawbacks; namely, an inevitable production of wastewater from washing process of catalyst residues and unreusability of the catalysts (Macleod et al., 2008). The heterogeneous catalytic process overcomes the homogeneous one since the solid catalysts can be easily recovered and therefore potentially be reusable. Besides, a neutralization step with large amount of wastewater production would be eliminated (Kawashima et al., 2008). Several heterogeneous catalysts have been employed in the biodiesel production, for example MgO, CaO, and hydrotalcites (Liu et al., 2007; Serio et al., 2007; Zabeti et al., 2009). CaO is closely resembled to an environmental-friendly material. Generally, Ca(NO3)2 or Ca(OH)2 is the raw material to produce CaO. Besides, there are several natural calcium sources from wastes, such as egg-

* Corresponding author. Tel.: +66 2 564 7100x6638; fax: +66 2 564 6981. E-mail address: kajornsak@nanotec.or.th (K. Faungnawakij). 0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2009.12.079

shell, mollusk shell, and bone. Using wastes as raw materials for catalyst synthesis could eliminate the wastes and simultaneously produced the catalysts with high cost effectiveness. In fact, the agricultural and food industries are the large private sectors in Thailand. To our knowledge, the waste shells of egg and mollusk from those industries were produced several tons a day. Recently, Nakatani et al. (2009) examined transesterication of soybean oil catalyzed by combusted oyster shell, and found that it is active for biodiesel production. Wei et al. (2009) and Boey et al. (2009) reported that eggshells and mud crab shell could be used as a catalyst for biodiesel production, respectively. All these works revealed that the waste shell-derived catalyst showed high potential to be used as a low-cost biodiesel production catalyst. Searching for the alternative resource for low-cost catalyst synthesis is therefore very attractive. A comparative study on correlation between the characteristics of the catalysts and the catalytic activity together with the optimization of the catalyst preparation and the reaction conditions would also be essentially useful for realizing this approach. In the present investigation, two types of waste mollusk shells, golden apple snail shell and meretrix venus shell, and waste eggshell were proposed as biodiesel production catalysts. The catalysts were tested in transesterication of palm olein oil. The characteristics of the catalysts derived from those wastes and their catalytic activities were investigated, while the comparison study of the catalysts derived from eggshell and mollusk shell as well as commercial CaCO3 on biodiesel production was also discussed.

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2. Methods 2.1. Materials and catalyst preparation Palm olein oil was obtained from commercial source in Thai market. The composition of fatty acid in the oil was found to be: C12:0 0.4%, C14:0 0.8%, C16:0 37.4%, C16:1 0.2%, C18:0 3.6%, C18:1 15.8%, C18:2 11.1%, C18:3 0.3%, C20:0 0.3%, and C20:1 0.1%. The analytical grade methanol (Fluka) was used in the transesterication. Waste shells of egg and mollusk as well as commercial CaCO3 (as a reference catalyst) were transformed to CaO catalyst by calcination in air at 800 C for 4 h. All catalysts were kept in the close vessel to avoid the reaction with air prior to subsequent usage. 2.2. Material characterization The waste shells were analyzed by thermo-gravimetric/differential thermal analyzer (TG/DTA; TGA/SDTA 851e, Mettler Toledo, Switzerland) under air ow condition with ramping rate of 10 C min1 to determine thermal transition of the samples. The crystalline phases of calcined samples were analyzed by X-ray diffraction (XRD; JDX-3530, JEOL, Japan) coupled with Cu ka radiation source. The elemental compositions were determined by energy dispersive X-ray uorescence spectroscopy (EDXRF; EDX-720, Shimadzu, Japan) under vacuum mode for precise measurement. The samples were characterized by scanning electron microscope (SEM; S-3400, HITACHI, Japan) and N2 adsorption (BELSORP-max, BEL, Japan) for their morphology and BET surface area, respectively. 2.3. Transesterication reaction procedure The transesterication was carried out in a batch reactor. A 50 ml of palm olein oil in a 500 ml round-bottom ask equipped with a reux condenser was stirred at 60 C. A mixture of methanol and catalyst at a designated amount heated at 60 C was added to the oil, and the transesterication was conducted for the required reaction times. The catalyst content was xed at 10 wt.%. Upon the reaction completion, the catalyst was separated from biodiesel product by centrifugation, and then excessive amount of methanol was evaporated before analysis of biodiesel yield. It should be noted that the duplicate experiments were performed, and the errors of % FAME contents were typically within 2.0 wt.%. 2.4. Determination of biodiesel yield The compositions of biodiesel were determined by a gas chromatograph (GC-2010, Shimadzu) equipped with capillary column, DB-WAX (30 0.15 m) and a ame ionization detector. Methylheptadecanoate was used as internal standard for quantication, according to EN14103. The biodiesel yield was characterized in term of % FAME as a function of time. The acid value of palm olein oil before and after the reactions was measured by potentiometric titration (Titrando, Metrohm, USA), according to ASTM D664.

3. Results and discussion 3.1. Material characterization The shells were analyzed by TG/DTA to determine the suitable calcination temperature for catalyst preparation. Only single dominant step of weight loss (ca. 50%) was found for all samples at the temperature range of 700850 C. Above 850 C, the weight of the sample remained almost constant, whilst the peak maxima in the DTG curves was found around 810830 C. The eggshell and mollusk shells are generally known to contain CaCO3 as a main Cabased component. The high temperature range above 700 C is required to transform CaCO3 to CaO, which could be conrmed by the TG and DTG curves. In the viewpoint of preparation time and energy consumption, the temperature of 800 C was selected as a suitable condition to produce CaO catalysts from the shells. XRD patterns of the shell-derived catalyst samples calcined at 800 C for 4 h exhibited similar results to those by Wei et al. (2009). All catalyst samples showed clear and sharp peaks identically. The peaks are subjected to a single crystalline phase of CaO. As shown in Table 1, the BET surface area of catalysts synthesized from eggshell, golden apple snail shell, and meretrix venus shell was as low as 1.1, 0.9, and 0.5 m2 g1, respectively. All shell-derived catalysts were considered to be less-porous materials due to their trace pore volume. The different value of SBET of each catalyst could be explained by SEM observation (results not shown). The calcined eggshell was rod-like particles and some of them were bonded together as aggregates. The calcined golden apple snail shell showed similar particle morphology, but larger size of aggregates. The largest size of aggregated particles was observed in the calcined meretrix venus shell. The smaller size of the grains and aggregates could provide higher specic surface areas. Since all samples are considered to be less-porous or even non-porous, the size of the particle should directly respond to the surface area. As also summarized in Table 1, all shell-derived catalysts were mainly composted of Ca, Si, S, and Sr species. Majority of all catalyst above 98% was from Ca species. The descending order of Ca content in the catalysts was ranked as follows: eggshell (99.21) > golden apple snail shell (99.05) > meretrix venus shell (98.59). 3.2. Biodiesel production activity In the heterogeneous transesterication, the palm olein oil or triglyceride was mixed with methanol and catalyzed by alkaline earth oxide; CaO in this case. Such triglyceride was catalyzed to di- and mono-glyceride, subsequently, while biodiesel (or fatty acid methyl ester) was produced simultaneously. At complete conversion, only biodiesel and glycerol were co-existed in the process as reaction products. The calcium methoxide species, Ca(CH3O)2, was reported to form on the surface of CaO catalyst, and enhanced the reaction between palm oil and methanol (Gryglewicz, 1999). Fig. 1 depicts the reaction time-dependence of FAME yield obtained in transesterication over catalysts derived from eggshell, golden apple snail shell, and meretrix venus shell. All catalyst samples exhibited the high FAME yield greater than 90% after reaction

Table 1 Elemental chemical compositions (atomic percentage), BET surface area (SBET), and total pore volume of the waste shell-derived catalysts calcined at 800 C for 4 h. Source of catalyst SBETa (m2 g1) Total pore volumea (cm3 g1) Composition (%)b Ca Eggshell Golden apple snail shell Meretrix venus shell
a b

Si 0.4 0.4 0.6

S 0.3 0.3 0.4

Sr 0.1 0.2 0.3

Others 0.0 0.1 0.1

1.1 0.9 0.5

0.005 0.004 0.002

99.2 99.0 98.6

Determined by N2 adsorption analysis. Determined by EDXRF analysis.

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100

80

60

40

20

Egg ....................................... Golden apple snail ....................................... ....................................... Meretrix venus

20 40 60 80 100 120

The effect of methanol/oil molar ratios on FAME yield over meretrix venus shell-derived catalyst (calcined for 4 h) was investigated. The FAME content increased signicantly by increasing the methanol/oil ratio from 9 to 12. This higher amount of methanol would promote the formation of methoxy species on CaO surface, and should also shift the reaction equilibrium to the forward direction. However, further increase in methanol/oil ratio up to 18 did not promote the reaction. It was considered that the glycerol would largely dissolve in excessive methanol and subsequently inhibited the reaction of methanol to the reactants and catalyst. The optimum MeOH:oil ratio was 12:1 over the catalyst in the present study, which was double the practical MeOH:oil ratio for homogeneous transesterication of 6:1. 4. Conclusions The CaO catalysts derived from eggshell, golden apple snail shell, and meretrix venus shell were elucidated to become active in heterogeneous transesterication for biodiesel production. The descending order of the catalytic activity over the shell-derived catalysts was as follows: eggshell > golden apple snail shell > meretrix venus shell. After simple calcination at 800 C, all shell-derived catalysts mainly consisted of CaO phase with high crystallinity as conrmed by XRD. Among three raw materials, the catalyst synthesized from eggshell showed the highest Ca content and highest surface area with smallest particle size, which could be the reasons of highest biodiesel yield. The present work clearly showed the potential use of three waste shell-derived catalysts for biodiesel production. Acknowledgements Authors acknowledged the NANOTEC for nancial support to the Nano Energy and Catalysis Laboratory, NANOTEC and to the project NN-B-21-FN7-93-52-20. References
Bach, U., Lupo, D., Comte, P., Moser, J.E., Weissortel, F., Salbeck, J., Spreitzer, H., Gratzel, M., 1998. Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon-to-electron conversion efciencies. Nature 395, 583585. Boey, P.-L., Maniam, G.P., Hamid, S.A., 2009. Biodiesel production via transesterication of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst. Bioresour. Technol. 100, 63626368. Faungnawakij, K., Kikuchi, R., Shimoda, N., Fukunaga, T., Eguchi, K., 2008. Effect of thermal treatment on activity and durability of CuFe2O4 and Al2O3 composite catalysts for steam reforming of dimethyl ether. Angew. Chem. Int. Ed. 47, 93149317. Gryglewicz, S., 1999. Rapeseed oil methyl esters preparation using heterogeneous catalysts. Bioresour. Technol. 70, 249253. Helwani, Z., Othman, M.R., Aziz, N., Kim, J., Fernando, W.J.N., 2009. Solid heterogeneous catalysts for transesterication of triglycerides with methanol: a review. Appl. Catal. A 363, 110. Kawashima, A., Matsubara, K., Honda, K., 2008. Development of heterogeneous base catalysts for biodiesel production. Bioresour. Technol. 99, 34393443. Liu, Y., Lotero, E., Goodwin Jr., J.G., Mo, X., 2007. Transesterication of poultry fat with methanol using MgAl hydrotalcite derived catalysts. Appl. Catal. A 331, 138148. Macleod, C.S., Harvey, A.P., Lee, A.F., Wilson, K., 2008. Evaluation of the activity and stability of alkali-doped metal oxide catalysts for application to an intensied method of biodiesel production. Chem. Eng. J. 135, 6370. Nakatani, N., Takamori, H., Takeda, K., Sakugawa, H., 2009. Transesterication of soybean oil using combusted oyster shell waste as a catalyst. Bioresour. Technol. 100, 15101513. Pinto, A.C., Guarieiro, L.L.N., Rezende, M.J.C., Ribeiro, N.M., Torres, E.A., Lopes, W.A., Pereira, P.A.P., Andrade, J.B., 2005. Biodiesel: an overview. J. Braz. Chem. Soc. 16, 13131330. Serio, M.D., Cozzolino, M., Giordano, M., Tesser, R., Patrono, P., Santacesaria, E., 2007. From homogeneous to heterogeneous catalysts in biodiesel production. Ind. Eng. Chem. Res. 46, 63796384. Wei, Z., Xu, C., Li, B., 2009. Application of waste eggshell as low-cost solid catalyst for biodiesel production. Bioresour. Technol. 100, 28832885. Zabeti, M., Wan Daud, W.M.A., Aroua, M.K., 2009. Activity of solid catalysts for biodiesel production: a review. Fuel Process. Technol. 90, 770777.

FAME (%)

0 0

Reaction time (min)

Fig. 1. Reaction time-dependence of FAME yield obtained in transesterication over catalysts derived from waste shells. Transesterication conditions: temperature = 60 C, methanol/oil molar ratio = 18:1, catalyst amount = 10 wt.%.

time of 2 h despite the fact that the conversion rates were different among the catalysts. The descending order of the conversion rate over the catalysts was ranked as follows: eggshell > golden apple snail shell > meretrix venus shell. The catalytic activity of the catalysts agreed well with the specic surface area and catalyst particle size. The higher SBET with smaller size of catalyst particles could provide higher reaction conversion. The basic site of the CaO catalyst is generally known to be active species in heterogeneous transesterication and the amount of the basic sites should depend on the surface area. Additionally, the transesterication activity agreed well with the Ca content in the catalyst samples; namely, the higher Ca content in the form of CaO resulted in the higher activity. It should be noted that the catalysts synthesized from eggshell and golden apple snail shell could give the biodiesel yield over than 95%. The reference catalyst showed comparable activity to the eggshell-derived catalyst. The palm olein oil used as a raw material for biodiesel production possesses low acid value of 1.10 KOH/g oil, whilst the nal biodiesel products have low acid value of ca. 0.20(0.05) KOH/g oil. The acid values meet the ASTM D664 standard (60.50 KOH/g oil). This result suggested that the waste shell-derived catalysts provided good potential for heterogeneous biodiesel production.

3.3. Effect of calcination time and methanol/oil ratio The effect of calcination time (0.5, 2, 4, and 8 h) on FAME yield over meretrix venus shell-derived catalyst was investigated. It was found that calcining the sample for 0.5 h was not enough to give highly active catalyst for the reaction. The calcined samples for 24 h exhibited comparable activity throughout the reaction course. However, further increase in calcination time inversely suppressed the catalytic activity of the catalyst. The prolonged treatment process would bring about the sintering of the catalyst and therefore the lowering of the surface area. The shrinkage of the catalyst grains would eventually suppress the active sites. The optimum calcination time was 24 h over the catalyst in the present study. This condition would be optimum for other waste shells since the thermal analysis (TG) showed almost identical behaviors. The higher temperature is not preferable due to the severe sintering rate and the high energy consumption.