Fuel 116 (2014) 267272

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Fuel
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Chitosan-catalyzed biodiesel synthesis: Proof-of-concept and limitations

Henning Kayser, Fabian Pienko, Pablo Domnguez de Mara
Institut fr Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringerweg 1, 52074 Aachen, Germany

h i g h l i g h t s
 Chitosan-aerogels catalyze biodiesel-

g r a p h i c a l a b s t r a c t

type transesterications.
 Chitosan is presently a waste that can

be valorized.
 Other polysaccharides (e.g. alginic

acid) may be used as catalysts as well.

a r t i c l e

i n f o

a b s t r a c t
Second generation biodiesel uses cooking oil wastes, vegetal oils cultivated in marginal lands, or algaebased oils. The quest of heterogeneous catalysts for biodiesel synthesis is motivated by the option of by-passing saponication and neutralization steps, enabling proper catalyst recoveries, and performing esterications and transesterications simultaneously, as impure waste oils contain a signicant concentration of free fatty acids (FFA). This paper evaluates the use of chitosan-cryogels as catalysts for (trans)esterication reactions of different oils with methanol. Being a worldwide available waste material, the use of chitosan as catalyst for biofuel production might add novel possibilities for the valorization of local areas. Chitosan-cryogels catalyzed successfully the transesterication of triolein and soybean oil with methanol to afford biodiesel yields of up to 90% (FAME) in 832 h at 100150 C. Chitosan beads could be partially recycled by washing them with tert-butanol and methanol to desorb fats and glycerol. To reach a practical use, further opportunities for research and development can be identied at the level of catalyst design, delivering chitosan-based novel catalysts e.g. aerogels, layers, chitosan-based derivatizations, etc. , that could enable more efcient catalytic rates and would display largely improved recyclability outcomes. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 5 July 2013 Received in revised form 5 August 2013 Accepted 6 August 2013 Available online 20 August 2013 Keywords: Biodiesel Chitosan Heterogeneous catalysis Waste valorization

1. Introduction The transesterication of biomass-derived triglycerides with short-chain alcohols (e.g. methanol or ethanol) is a largely implemented industrial process giving access to biogenic glycerol and fatty acid methyl esters (FAMEs) [1]. FAMEs can be directly used as biodiesel for ground transportation, or after hydrogenation they may serve as potential aviation biofuels (HVO) [1,2]. Addressing sustainability issues (deforestation of rainforest areas, food competition etc.), biodiesel segment is slowly changing from the so-called rst generation biodiesel based on vegetal oils, e.g. palm, sunower or soybean oils to the second generation one, focusing
Corresponding author. Tel.: +49 241 8020468; fax: +49 241 8022177.
E-mail address: dominguez@itmc.rwth-aachen.de (P. Domnguez de Mara). 0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.08.013

on waste raw materials like cooking oil wastes, vegetal oils that are harvested in marginal lands, such as jatropha, or algae-based oil raw materials [1,2]. From a broad vista for the coming years, it may be expected that 1st generation biodiesel will have less preponderance, whereas second generation resources will emerge as a future important alternative fuel for the valorization of local resources and wastes, contributing to energy cost savings and to less external dependency on fossil-based fuels suppliers. Apart from these obvious ecological and geopolitical considerations, the economic aspects of biodiesel production are obviously a key-issue for its sustainable preparation as well. Typically, conventional biodiesel is straightforwardly produced by means of homogeneous alkaline catalysts, such as NaOH, KOH, or methanolate species dissolved in methanol [14]. These systems are very efcient for transesterications, yet at the cost of an energy-inten-

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sive catalyst production (amalgam process, chlorinealkaline electrolysis). Moreover the generation of considerable amounts of wastewater during the neutralization and separation of the catalysts from the formed biodiesel is virtually unavoidable. Likewise, homogeneous alkaline catalysts are markedly sensitive to free fatty acids (FFA), leading to saponication problems and catalyst losses. While FFAs do not represent a signicant hurdle in (pure) vegetal oils with rather low quantities of such FFAs , it becomes certainly a challenging issue when the production of second generation biodiesel is intended, as the content in FFA of such (impure) oil wastes could be in the range of even up to 5% w/w [36]. Herein, basic homogeneous catalysts suffer saponication, lowering the efciency and economics of the overall process, and making biodiesel production less appealing. To circumvent these issues, some industrial chemical plants incorporate an acid-catalyzed pre-step (typically using H2SO4 as catalyst) to rstly form FAMEs from these FFAs. Later on, the base-catalyzed step carries out the actual transesterication-based biodiesel synthesis. Obviously, the setup of a pre-step unit complicates the process and leads to tighter economic gures, as reported by several studies [36]. Another approach to solve problems derived from the presence of FFAs is the incorporation of heterogeneous catalysts that could catalyze both trans- and esterication reactions at the same time. Furthermore, heterogeneous catalysts might simplify downstream processing operations separations, neutralizations, etc. , as well as enabling the reuse of the catalysts with a diminished waste formation. On this basis, an ample range of heterogeneous catalysts have been assessed for the production of biodiesel [36]. Among them, lipases under different (mild) reaction conditions [7,8], as well as guanidinium-based immobilized organocatalysts (as organic bases) are remarkable examples that have been successfully put forth [9]. Actually, several production plants using immobilized lipases as biocatalysts for biodiesel synthesis have already reached commercialization [10]. Envisaging the increasing future needs of local but worldwide available and inexpensive materials that might serve as basis for catalysts for large-scale applications, this paper explores the use of chitosan as organocatalyst for biodiesel-type (trans)esterication reactions. Chitosan is a worldwide largely abundant polysaccharide derived from chitin (poly(b-(1?4)-N-acetyl-D-glucosamine) by deacetylation of the amide groups, thus leading to a polymer bearing basic amino functions (pKa  6.5) in its backbone (Fig. 1) [11]. Chitosan is obtained through deacetylation of chitin, and mostly discarded as a waste at ton scale from shellsh industries. Considerable research has been undertaken for the valorization of chitosan, and among other options chitosan has found a promising use as a support for catalyst immobilization, with a broad number of applications in different chemical reactions [12]. Notably, by directly looking at chitosan itself, it could be presumed that the presence of a large amount of free amino groups might confer chitosan promising (heterogeneous) catalytic properties. Surprisingly, the assessment of chitosan as catalyst (as such) has been rather scarce, with only some recent successful results in aldol-catalyzed CC

bond formation among aldehydes and ketones, and analogous condensation reactions [1316]. For these examples, chitosan-aerogels are typically formed, aiming at enhancing the specic surface of the catalyst and the amount of accessible amino groups for an adequate catalysis [1316]. Apart from the use of chitosan in these C C bond forming reactions, chitosan has hardly been tested for (trans)esterication-based reactions, with only one paper reporting on the esterication of glycidol with carboxylic acids, leading to moderate results [17]. For biodiesel synthesis some articles reported the adsorption on chitosan of different catalysts, namely inorganic oxides (e.g. CaO) [18,19], but to our knowledge no studies assessing chitosan as catalyst for biodiesel synthesis has been disclosed in the scientic literature so far. As it can be rapidly inferred, being chitosan a rather worldwide and inexpensive waste material, their direct use as heterogeneous organocatalyst for biodiesel synthesis might contribute to the valorization of local areas in which chitosan and oil-based wastes are present at large scale. Having these considerations in mind, in this paper the proof-of-concept of using chitosan-cryogel beads as catalysts for (trans)esterication-based biodiesel synthesis is reported. Moreover, critical assessments on important reaction parameters (temperature, methanoloil ratio, kinetics and reusability of the catalyst) are evaluated as well, clearly delimiting the potential advantages of chitosan as catalyst for large-scale reactions, and pinpointing at the same time a number of limitations that will require further research and optimizations, especially at the level of catalyst design, to enable practical processes using wastes as biodegradable catalysts.

2. Materials and methods 2.1. Chemicals Soybean oil, triolein, and chitosan from shrimp shells were obtained from Sigma Aldrich. Methanol was puried by distillation. Any other chemicals were used without any further purication.

2.2. Production of chitosan-cryogels Cryogel beads were prepared as reported elsewhere [13] by freezing hydrogel beads to 5 C and removing water by lyophilization (2 103 mbar) until constant weight (12 weeks). Previously the hydrogel beads were obtained by dissolving 2.5 g chitosan (from shrimp shells, >75% deacetylated) in an aqueous acetic acid solution (5.5 mM; 100 mL). The solution was drop-wise precipitated through a 2 mm syringe into an aqueous NaOH solution (0.1 M; 300 mL). After 2 h, the hydrogel beads were ltrated over sintered glass crucible and washed with deionized water until constant pH was reached. The resulting beads were stored in water overnight and washed with 23 L deionized water before ltrating.

2.3. Standard reaction conditions 3 g Methanol, 200 mg of triolein/soybean oil and 20 mg chitosan-cryogel beads were added in closed 10 mL microwave vessel. The reaction mixture was magnetically stirred.

2.4. Esterications Direct esterications of 200 mg linoleic acid were carried out in 10 mL high pressure reactors at 130 C for 12 h with 20 mg chitosan-cryogel beads and 3 g methanol. Conversions were determined by 1H NMR.

Fig. 1. General structure of chitin (R = Ac)/chitosan (>75% R = H) [11].

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2.5. Recycling experiments The catalyst beads were ltered off the reaction mixture in a glass crucible and washed with 3 10 mL MeOH and 3 10 mL DCM. Before re-use the residual eluent was stripped off under high vacuum. Washing the used beads in 3 10 mL tBuOH and stirring them in 5 mL tBuOH at room temperature overnight before applying the above mentioned washing procedure with MeOH lead to increased activity in the subsequent cycles. 2.6. GC analysis The yield was determined by gas chromatography (Siemens GC; CP-Sil-8-CD wax column, 25 m, Df: 0.52 lm; bore: 0.32 mm; FID detector) from the crude reaction mixture. Methyl margarate (17:0) was added as internal standard. Temperature program: 5 min 80 C iso, 8 C/min, 280 C iso-methyl palmitate (16:0); methyl oleate, methyl lineate (18:1 and 2) and methyl stearate (18:0) could be separated individually. 3. Results and discussion To enhance the amount of amino groups accessible for catalysis, following rationale and results reported in previous literature [13,16], chitosan-cryogel beads were prepared in a solgel method followed by lyophilization, as described for aldol condensation reactions (see also experimental part) [13]. In a rst set of experiments, the chitosan-cryogels-catalyzed transesterication of triolein and soybean oil as prototypical oil raw materials , with methanol was studied as model reaction in a microwave reactor (300 W) at 120 C. Results are depicted in Fig. 2. At 120 C chitosan-cryogels (with catalyst loadings of 0.5 wt%) successfully catalyzed the transesterication of different triglycerides with methanol to afford FAMEs in high yields (up to 90%). Reaction rates observed for triolein entirely composed of oleic acid were much faster than those of soybean oil as substrate. Thus, FAME yields of up to 90% were reached in 912 h for triolein (3 double bonds per triglyceride) under the reported non-optimized conditions (Fig. 2). The use of soybean oil (more unsaturations per triglyceride) also led to such high FAME yields, albeit at longer reaction times (2432 h). Average compositions of fatty acids in soybean oil are 11% palmitate (16:0), 4% stearate (18:0), 23% oleate (18:1), 53% linoleate (18:2) and 8% linolenate (18:3), leading to an overall average of 4.7% double (unsaturated) bonds per triglyceride [20,21]. This composition could be conrmed by gas chromatographic analysis of the used oil samples. It could be hypothesized that the existence of different kinetic patterns for transesterications, depending on the fatty acid

(saturated, mono- or di-unsaturated) might explain such differences in reaction rates observed for both oils. Overall, results achieved are promising taking into account that catalyst loadings were approximately one order of magnitude lower than many other heterogeneous catalysts reported for biodiesel synthesis in the literature (0.5 wt% for chitosan vs. 510 wt% typically reported) [3,4]. However, experiments conducted at higher chitosan-aerogels loadings led to severe swelling and mass-transfer limitation problems. Importantly, chitosan is known to be a widely malleable material, from which layers, beads or other different forms and textures can be created in a straightforward way [12]. Therefore, there should be the potential to design improved highly-loaded chitosan-based catalysts specically for biodiesel synthesis. An important aspect in transesterication-based biodiesel synthesis is the ratio methanoloil that is applied in the reaction system, especially when solvent-free approaches are envisaged. Stoichiometrically the complete transesterication of a triglyceride demands 3 equivalents of methanol. Obviously, a number of intermediates like di- or mono-glycerides will be formed during the biodiesel synthesis. Therefore, to trigger the reaction to a selective FAME formation with glycerol as by-product , a large surplus of alcohol is typically loaded in the reaction mixture. Apart from thermodynamic reasons, an excess of alcohol also enables better rheological conditions for the reaction (e.g. less viscosities), limiting mass transfer limitations. Importantly, methanol and ethanol are distillable and recoverable once FAME is formed, largely contributing to economics of the process. Taking this into account, reaction conditions for chitosan-catalyzed biodiesel synthesis were more carefully studied with regard to such methanoloil ratio, under the same catalyst loadings (Fig. 2), and again in microwave reactors (300 W) at 120 C. In this case, soybean oil was used as prototypical substrate. Results are depicted in Fig. 3. As expected, a large surplus of methanol compared to soybean oil was needed to reach acceptable synthetic rates. At lower methanol-to-oil ratios the viscosity of the mixture increased signicantly, and swelling effects were observed for the chitosan beads, leading to some rheological problems in the reaction set-up. Albeit methanol is distilled and reused in biodiesel plants as it is typically used in excess , it may be expected that a better catalyst design of chitosan (e.g. in layers, with less polymerization degrees, etc.) [12] might certainly improve the data herein reported, providing more competitive synthetic performances at lower methanol concentrations. In these experiments (Figs. 2 and 3), temperature had been arbitrarily set at 120 C. Subsequently, the inuence of the

Fig. 2. Chitosan-cryogels-catalyzed transesterication of triolein and soybean oil with methanol. Conditions: 10 mL microwave reactor (300 W), 120 C, 20 mg dried chitosan-cryogels (0.5 wt%), 200 mg triolein, 3 g methanol. FAME yield determined by GC (see experimental for details). Experiments without chitosan showed very low biodiesel formation at 120 C (see also Fig. 4 in this paper).

Fig. 3. Inuence of the alcoholoil ratio (w/w) in the chitosan-catalyzed transesterication of soybean oil and methanol. Conditions: 10 mL microwave reactor (300 W), 120 C, 12 h, 20 mg dried chitosan-cryogels, 3 g methanol, variable amounts of soybean oil. FAME yield determined by GC (see experimental for details).

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Fig. 4. Inuence of the temperature in the chitosan-catalyzed transesterication of soybean oil and methanol. Conditions: 10 mL microwave reactor (300 W), different temperatures 90190 C, 12 h, 20 mg dried chitosan-cryogels, 3 g methanol, 200 mg soybean oil. FAME yield determined by GC (see experimental for details). Black columns: reaction with chitosan; gray columns: blank reactions without catalyst.

Fig. 5. Recycling of chitosan-aerogels. Conditions: 10 mL microwave reactor (300 W), 120 C, 12 h, 20 mg dried chitosan-cryogels, 3 g methanol, 200 mg triolein. FAME yield determined by GC (see experimental for details).

temperature in the chitosan-catalyzed was studied. Likewise, catalyst-free blank reactions were performed as well. Results are depicted in Fig. 4. As can be observed, the chitosan-catalyzed transesterication rates of soybean oil started to be signicant at temperatures in the range of 100150 C, which provides a promising framework to set-up reactions at mild reaction conditions, whereby degradation of unsaturated fatty acids or chitosan itself, as well as other by-product formation should not be expected. Some background reaction (catalyst-free) were observed only at temperatures higher than 150 C [22]. As stated above, one of the potential advantages of using heterogeneous catalysts is that esterication and transesterication may be conducted at the same time, provided that such heterogeneous catalysts may catalyze both reactions. In these cases, saponications observed in homogeneous alkaline catalysts would be overcome, thus leading to a simplied and cleaner process set-up (e.g. no need of a pre-step of acid-catalyzed esterication) [3,4]. Furthermore, there would not be need of setting an acid-catalyzed pre-step for esterications, simplifying the process set-up as well. As stated above, this aspect is of utmost importance for second generation biodiesel, whereby impure oils (e.g. wastes of cooking oil) containing signicant amounts of FFA (up to 5% w/w) may be present [3,4]. Thus, esterication reactions with chitosan-cryogels were conducted as well, using linoleic acid and methanol as substrates. Albeit conversions were not high, chitosan derivatives were actually able to catalyze esterications under those reaction conditions as well, thus allowing the use of them for second generation biodiesel (Scheme 1) in a combined (trans)esterication process. Finally, preliminary experiments in catalyst reuse were performed. According to literature, there is a high afnity of chitosan to fats and triglycerides, which are adhered onto the polysaccharide backbone [23]. Therefore, chitosan-cryogel beads must be washed after each catalytic cycle. Considering the lipophilic nature of fats, it may be expected that non-polar solvents (e.g. dichloromethane, or alkanes) would be useful for that. Yet, even if successful, the use of hazardous petroleum-based solvents could lead to environmental concerns for a large-scale application in bioreneries. Considering these potential ecological issues, tert-butanol was

also assessed as solvent for washing chitosan beads among catalytic cycles. Despite a petroleum-based route based on isobutylene is currently applied for the production of tert-butanol at industrial scale, very recently fermentative approaches for isobutylene synthesis based on glucose as raw material have been reported, with promising economics for the future delivery of a biomass-derived isobutylene [25]. In principle, tert-butanol should display an adequate lipophilic prole, while at the same time being a distillable and easy-to-handle solvent. Taking the bench reaction conditions set in this paper (Figs. 2 and 3), in one set of experiments, chitosan-cryogels were washed with methanol and then with dichloromethane (DCM) (see experimental part for details), before using them again in the next catalytic cycle. In parallel, in a second set chitosan-cryogels were washed with tBuOH and methanol, and then reused again. Results are depicted in Fig. 5. In both strategies a loss of activity is observed among reaction cycles during biodiesel synthesis. For other reactions (e.g. aldol CC bond formation), chitosan-cryogels remained stable during more catalytic cycles [13]. Remarkably, the washing steps with methanol and non-polar DCM did not lead to any successful outcome, and chitosan-cryogels were completely deactivated from in one cycle, presumably to the adsorption of fats and glycerol to the polysaccharide [23]. Interestingly, applying the novel tBuOH methanol washing strategy, more satisfactory results (albeit still largely non-optimized) were reached, and chitosan-cryogels still maintained certain activity in transesterication reactions after 4 cycles. Analogous results have been observed when washing immobilized lipases with tBuOH after biodiesel synthesis [24]. Despite chitosan is an inexpensive material, these washing-recycling strategies need obviously to be largely improved to envisage a practical application in the generation of low-added-value products, such as biodiesel. Taken together, however, these results represent the rst proof-of-principle of using chitosan as catalyst for the valorization of local areas. A number of opportunities for catalyst design and process development using chitosan-catalysts may be foreseen for future research, to nally validate whether such polysaccharides can be used as efcient catalysts. Encouraged by the observed capability of chitosan a natural polysaccharide to act as catalyst for transesterication reactions,

Scheme 1. Esterications catalyzed by chitosan. Conditions: 10 mL high pressure reactor; 130 C; 12 h; 20 mg chitosan-cryogel beads; 200 mg linoleic acid; 3 g methanol; Conversion was determined by 1H NMR. Blank reactions did not afford any ester production.

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Scheme 2. Alginic-acid-catalyzed transesterication of soybean oil and methanol to afford FAMEs. 10 mL high pressure reactor; 130 C; 12 h; 20 mg alginic acid; 200 mg soybean oil; 3 g methanol; FAME yield determined by GC (see experimental for details).

the focus was put on another natural polysaccharide namely alginic acid , which is also widely available worldwide from algae resources [11]. The capability of alginic acid as catalyst for biodiesel synthesis was assessed in the same reaction conditions as well (Scheme 2). Gratifyingly, alginic acid can also act as a catalyst for biodiesel-type transesterication reactions, yielding up to 80% FAME yield in the conditions assessed.

additional support of the Cluster of Excellence Tailor-Made Fuels from Biomass is gratefully acknowledged.

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4. Conclusions Among other biofuels, second generation biodiesel with focus on wastes, used cooking oil, and vegetal oils cultivated in marginal lands is expected to have a practical application in the coming decades, especially for the local valorization of resources. Chitosan is a readily available, inexpensive and non-hazardous polymer, typically discarded as a waste at large scale. This paper has successfully assessed the use of chitosan-cryogels as catalysts for biodiesel-type transesterications. Advantageous, chitosan-cryogels can be used directly as catalysts for the transesterication of different oils with methanol, with an operational frame of 100150 C and with yields of up to 90% FAME. Overall, results deliver a promising concept for using wastes and resources for the local valorization of resources. After this proof-of-concept and from a practical viewpoint, however, this paper has pinpointed several limitations that certainly need further research, development and optimization. Herein, one important point is the catalyst design to which chitosan may be handled and manufactured, e.g. formation of cryogels, layers, lower crystallinity, etc.). In addition, the delivery of expanded polymers that could enhance the amount of catalytic centers per area unit might certainly improve kinetics and catalytic performance. Likewise, some of these chitosan forms might provide better rheological conditions and lower swelling properties in reactor media, enabling the catalysis under more optimized methanol-to-oil ratios. Furthermore, albeit the reusability of the catalyst has proven to be feasible upon washing chitosan beads with tert-butanol, for large-scale applications to afford low-added value products, it becomes clear that much more optimized protocols need to be developed, affording a higher stability and activity of chitosan over much larger residence times. Overall, chitosan offers promising research avenues for bioreneries from waste-tovalue but much more research is needed to nally determine whether waste-chitosan may be used in local areas for the production of local biodiesel in a sustainable and environmentallyfriendly manner. Acknowledgements Mrs. Hannelore Eschmann and Ms. Julia Wurlitzer are thanked for support in analytical measurements (GC). Furthermore,

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