Bioresource Technology 100 (2009) 28832885

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

Application of waste eggshell as low-cost solid catalyst for biodiesel production

Ziku Wei a,b, Chunli Xu a,b,*, Baoxin Li c
a b c

Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, Xian 710062, PR China School of Chemistry and Materials Science, Shaanxi Normal University, Changan South Road 199, Xian 710062, PR China Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry and Materials Science, Shaanxi Normal University, Xian, 710062, PR China

a r t i c l e

i n f o

a b s t r a c t
Waste eggshell was investigated in triglyceride transesterication with a view to determine its viability as a solid catalyst for use in biodiesel synthesis. Effect of calcination temperature on structure and activity of eggshell catalysts was investigated. Reusability of eggshell catalysts was also examined. It was found that high active, reusable solid catalyst was obtained by just calcining eggshell. Utilization of eggshell as a catalyst for biodiesel production not only provides a cost-effective and environmental friendly way of recycling this solid eggshell waste, signicantly reducing its environmental effects, but also reduces the price of biodiesel to make biodiesel competitive with petroleum diesel. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 11 September 2008 Received in revised form 18 December 2008 Accepted 18 December 2008 Available online 7 February 2009 Keywords: Eggshell waste Biodiesel Catalysis Heterogeneous catalysis Transesterication

1. Introduction Eggshell weighs approximately 10% of the total mass (ca. 60 g) of hen egg, and eggshell is the signicant solid waste produced from food processing and manufacturing plants (Stadelman, 2000). In China, for example, it is estimated that annually about 4,000,000 tones is generated and will continue to grow in future (MOA, 2006). Most of the eggshell waste is commonly disposed in landlls without any pretreatment because it was traditionally useless (Tsai et al., 2008a). However, the waste management is not a desirable practice in view of the environmental odor from biodegradation (Tsai et al., 2008b). In recent years, a great deal of effort has been conducted for the application of eggshell as value-added products. These major applications included a possible bone substitute (Dupoirieux et al., 1995), the starting material for preparing calcium phosphate bioceramics (e.g., hydroxyapatite) (Balazsi et al., 2007), and a low-cost adsorbent for removal of ionic pollutant from the aqueous solution (Tsai et al., 2008a). Eggshell has a little developed porosity and pure CaCO3 as an important constituent. The chemical composition (by weight) of eggshell has been reported as follows: calcium carbonate (94%), magnesium carbonate (1%), calcium phosphate (1%) and organic matter (4%) (Stadelman, 2000). Due to its intrinsic pore structure in the calcied eggshell, high content of CaCO3 and the amount in abundance,
* Corresponding author. Address: School of Chemistry and Materials Science, Shaanxi Normal University, Changan South Road 199, Xian 710062, PR China. Tel.: +86 29 85300970; fax: +86 29 85307774. E-mail address: xuchunli@snnu.edu.cn (C. Xu). 0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2008.12.039

it is possible to prepare active heterogeneous catalyst from eggshell. However, to our best knowledge, there is no report about catalyst prepared from eggshell in the open literature. The price of petroleum diesel has soared in recent years and the available reserves of this important fuel will eventually be exhausted if large-scale use continues, and greenhouse gas emission by the usage of fossil fuels is also becoming a greater concern. So, research is now being directed towards the use of alternative renewable and environmentally friendly fuels that are capable of fullling an increasing energy demand (Ma and Hanna, 1999). Biodiesel is a renewable alternative to petroleum diesel that is composed of monoalkyl esters of fatty acids, and it has similar physical properties to petroleum diesel but unique advantages including being renewable, biodegradable, non-toxic and low emissions. Biodiesel is generally produced by transesterication of vegetable oils or animal fats with short-chain alcohols (generally methanol) in the presence of catalysts (Ma and Hanna, 1999; Di Serio et al., 2008; Huber et al., 2006). The conventional catalysts for this transesterication reaction are homogeneous strong bases (such as alkali metal hydroxides and alkoxides) and homogeneous acids (such as H2SO4). However, alkaline catalysts are generally corrosive to equipment and also react with free fatty acid to form unwanted soap by-products that require expensive separation; homogeneous acid catalysts are difcult to recycle and operate at high temperatures, and also give rise to serious environmental and corrosion problems. Therefore, the development of solid catalysts has recently gained much attention in view of their ease of separation and lack of corrosion or toxicity problems (Lpez et al., 2007; DaSilveira Neto et al., 2007). Unfortunately, the

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preparation of the highly effective solid catalysts is complex, costly, and requires experienced people to operate it (Zong et al., 2007). The cost of fabricating a catalyst can be a critical factor in its industrial applications. The production of biodiesel calls for an efcient and cheap catalyst to make the process economic and fully ecologically friendly, accordingly reducing its price and making it competitive with petroleum diesel (Di Serio et al., 2008; Kawashima et al., 2008; Zong et al., 2007; Toda et al., 2005). In this work, we explored the possibility of application of eggshell as a catalyst in catalytic process of biodiesel production. Reuse of eggshell as low-cost catalyst for biodiesel production was investigated in the viewpoint of the recycle of eggshell waste, minimization of contaminants, reducing the production costs of biodiesel and making the process to produce biodiesel fully ecologically friendly. 2. Methods 2.1. Materials Eggshell was collected from the local bakeries. To remove impurity and interference material, the eggshell was rinsed several times with deionized water. Then, the eggshell was dried at 100 C for 24 h in the dry oven. Calcination was performed in the mufe furnace at different temperatures (200 C1000 C) for 2 h under static air after crushing the dried eggshell. 2.2. Characterizations TGA experiments were carried out using Q600 SDT thermal analysis machine (TA Instruments, USA) under a ow of nitrogen. The sample weight used was about 20 mg, and the temperature ranged from 38 C to 1000 C with a ramping rate of 20 C min1. X-ray diffraction patterns were recorded on a D/Max-3C X-ray powder diffractometer (Rigalcu Co., Japan), using a Cu-K a source tted with an Inel CPS 120 hemispherical detector. SEM micrographs were performed using a Quanta 200 scanning electron microscope equipped with an energy dispersive spectrometer (Philips-FEI Co., the Netherlands). 2.3. Reaction procedure The reactions were carried out in a batch reactor at 65 C or 150 C under vigorous stirring. Typical reactions were performed with 25 ml of vegetable oil (100% soybean oil; Xian Jiali Grease Industrial Co., Ltd., Xian, China) and 9 ml of methanol (methanol/ vegetable oil molar ratio 9:1; molecular weight of soybean oil 871 g/mol was used) using 3 wt% (catalyst/oil weight ratio) of eggshell derived catalyst at 65 C for the specied time. The reaction products were analysed using the following procedure. The samples were separated from catalyst and glycerol by centrifuge. The glycerol could be separated because it was insoluble in the esters and had a much higher density. Then methanol was removed using a vacuum pump and the obtained product was added to deuterated chloroform for 1H NMR to determine the yield to methyl ester. 3. Results and discussion 3.1. Characterization of eggshell waste-derived catalysts The heterogeneous catalyst was prepared by calcining eggshell waste at high temperature. The textural structure of eggshell calcined at different temperatures can be observed from the scanning electron micrograph (SEM) images. Natural eggshell had macrop-

ores and a generally irregular crystal structure. The SEM images indicated that the structure of eggshell changed with calcination temperature. Below 700 C, the size and shape of particles was similar to that of natural eggshell. Above 800 C, the size of particles decreased and the particle shape became more regular. The change of structure of eggshell may be resulted from the change of composition. In order to explain the effect of calcination temperature, we investigated the calcination process of eggshell with thermal gravity analysis (TGA) technology. TGA result showed the temperatures, at which the eggshell precursors decomposed when heated in a controlled environment. Water and organics was removed from the precursors below 600 C, whereas carbon dioxide was lost between 700800 C. The thermal pre-treatment resulted in a change in the X-ray diffraction (XRD) pattern, caused by the removal of CO2 from the starting material (Fig. 1). The diffraction patterns of the samples heated at temperatures <700 C were characteristic of CaCO3, while samples activated at temperatures >700 C displayed diffraction reections characteristic of CaO. Samples calcined at 700 C for 2 h contain CaCO3 as the major phase and CaO as a minor phase. 3.2. Transesterication over eggshell waste-derived catalysts 3.2.1. Effect of calcination temperature To determine the inuence of the calcination temperature on the activity of the eggshell-derived catalyst, eggshell was calcined at different temperatures between 200 C and 1000 C and then

CaO CaCO3

Intensity (a.u.)

1000 C

900 C

800 C

700 C

Intensity (a.u.)

600 C

500 C

300 C

200 C

natural

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Fig. 1. XRD patterns of natural eggshell and the materials obtained by calcining natural eggshell in the range of 200 C1000 C.

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tested for the transesterication of soybean oil to produce biodiesel. These results showed that eggshell sample calcined above 800 C was the most active catalyst. A yield of 9799% was obtained in the presence of eggshell sample calcined above 800 C. When the calcination temperature was 700 C, a yield of 90% was achieved, whereas, a low level of activity was observed when the calcination temperature was <600 C. A yield of <30% was gained in the presence of eggshell sample calcined <600 C. The changes observed in the XRD patterns (Fig. 1) coincided with a change in the catalytic activity of eggshell calcined at different temperatures. Calcinations below 600 C did not lead to the formation of CaO, and, consequently, the catalytic activity was very low. The best catalytic performance was obtained for calcination temperatures above 800 C, when the XRD patterns showed a crystalline CaO. Samples calcined at 700 C for 2 h contain CaCO3 as the major phase and CaO as a minor phase, hence middle yield were obtained. Therefore, CaO were the active phase of the eggshell derived catalysts. 3.2.2. Effect of reaction variables The yield of biodiesel was affected by reaction variables, such as methanol/oil ratio, catalyst amount or reaction time. The reaction variables were associated with the type of catalysts used (Ma and Hanna, 1999). Therefore, the effect of reaction variables was studied in the presence of eggshell-derived catalyst. For the following reactions, all the catalyst was prepared by calcinning eggshell at 1000 C for 2 h. The experimental results showed that the yield increased with increasing the methanol/oil molar ratio, and reached a maximum when the ratio was above 9. When a small amount of catalyst (<1 wt%) was used, the maximum product yield could not be reached. However, increasing the amount of catalyst to more than 10 wt% lead to the slurry (mixture of catalyst and reactants) becoming too viscous, giving rise to a problem of mixing and a demand of higher power consumption for adequate stirring. To avoid this kind of problem, an optimum amount of catalyst loading was determined. The results showed that the yield increased with increasing the catalyst loading weight up to 3 wt%. However, the yield did not increase when the catalyst loading weight was above 3 wt%. Getting the reactants to and from the catalyst became the rate determining step (mass transport limitation) which was why adding more catalyst didnt have an effect. Therefore, the optimum catalyst loadings was found to be 3 wt% in this system. The effect of reaction time was tested. The results showed that the yield increased with time, reaching maximum value (yield >95%) after 3 h. The experimental results showed that a 9:1 molar ratio of methanol to oil, addition of 3 wt% eggshell-derived catalysts (calcined at 1000 C, CaO), 65 C reaction temperatures gave the best results, and the biodiesel yield exceeded 95% at 3 h. Both the reaction condition and yield of biodiesel were almost similar to that of homogeneous catalytic system (Ma and Hanna, 1999). Hence, eggshell-derived heterogeneous catalyst showed high activity. 3.2.3. Reusability of eggshell waste-derived catalysts We also investigated the reusability of the catalyst. The results indicated that the eggshell-derived catalyst can be repeated use for 13 times with no apparent loss of activity. After being used for more than 13 times, eggshell-derived catalyst lost activity gradually. The eggshell-derived catalyst was completely deactivated after being used more than 17 times. The deactivation of eggshell-derived catalyst may be ascribed to its structure change. The XRD patterns of the eggshell-derived catalyst used more than 17 times were characteristic of Ca(OH)2, while fresh eggshell-derived catalyst displayed diffraction reections characteristic of CaO. This showed that the major phase of catalyst has changed from CaO (fresh catalyst, Fig. 1) to Ca(OH)2 (catalyst used more

than 17 times). The structure change of catalyst could result from the reaction between H2O and CaO, because the reactants (soybean oil and methanol) contain a little amount of water. However, the catalyst can be regenerated just by simple calcination. Therefore, eggshell-derived catalyst can be reused and regenerated. 4. Conclusions High active, reusable solid catalyst was obtained by just calcining eggshell. Calcined eggshell exhibited high activity towards the transesterication of vegetable oil with methanol to produce biodiesel. The method of reusing eggshell waste to prepare catalyst could recycle the waste, minimizing contaminants, reducing the cost of catalyst, and making the catalyst environmentally friendly. This high efcient and low-cost eggshell catalyst could make the process of biodiesel production economic and fully ecologically friendly. The ecologically friendly and economic process could effectively reduce the processing cost of biodiesel, making it competitive with petroleum diesel. We anticipate that the low-cost catalyst could be used in a large-scale industrial process of biodiesel, making the process cheap and ecologically benign. In addition to biodiesel production, such environmentally benign eggshell-derived catalysts should nd application in a wide range of other base-catalysed important organic reactions. Acknowledgements This work was supported by the Scientic Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.biortech.2008.12.039. References
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