Transesterification of waste cooking oil using FeCl3-modified resin catalyst and the research of catalytic mechanism

doi:10.1016/j.renene.2015.08.079

Renewable Energy

Volume 86, February 2016, Pages 643-650

https://doi.org/10.1016/j.renene.2015.08.079 Get rights and content

Highlights

•
FeCl₃-modified resin used as catalyst to prepare biodiesel.
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Catalytic mechanism of modified resin was investigated.
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Modified resin can be reused easily and multiple.

Abstract

Biodiesel production from waste cooking oil using FeCl₃-modified resin as heterogeneous catalyst was investigated. In the optimum conditions, Fe load rate of resin of 10.97%. Comparison of effects of modified resin, unmodified resin, and homogeneous catalyst (FeCl₃·6H₂O) for the transesterification of waste cooking oil and methanol revealed that the transesterification rate of modified resin as catalyst reached 92.13%, which was 13.37% and 27.81% higher than those of unmodified resin and FeCl₃·6H₂O as catalysts, respectively. After the ninth run of reusing modified resin, transesterification rate stilled reach 73%. The result of NH₃-Fourier transform infrared analysis proved that FeCl₃ reacted with Bronsted acid site (SO₃H) to form a new Lewis acid site. Results of Fourier transform infrared and X-ray diffraction analyses showed that –OH group disappeared and no crystalline phase was present in modified resin, which illustrated that the new Lewis acid site was formed by chemical reactions.

Introduction

Depletion and scarcity of fossil oil resources inevitably threatens the national energy security. Various energy researches focused on the development of renewable and alternative energy sources to abate the dependence on fossil fuels [1]. The SO₂, NO_x, and a large number of particles produced from combustion of fossil fuels inflict serious environmental problems [2]. Biodiesel, a sulphur-free [3], nontoxic and biodegradable [4] renewable fuel, can greatly reduce the emissions of harmful gases and dust to the environment.

Biodiesel is generally produced via the transesterification of vegetable oils or animal fats with low molecular weight alcohols [5]. Currently, biodiesel is commercially produced using a homogeneous catalyst (NaOH, alkali catalysis; H₂SO₄, acid catalysis) for the transesterification process, because of its high reaction activity and low cost. However, the recovery of these soluble catalysts from the products of transesterification is time consuming and difficult [6]. In addition, during the homogeneous alkali catalysis process, the free fatty acids are readily saponified by the alkali catalysts (RCOOH + NaOH → RCOONa + H₂O), which not only lead to a huge loss of catalyst, but also to an increase in biodiesel purification cost [6], [7]. Meanwhile, the application of homogeneous acid catalysis in the transesterification step causes equipment corrosion and generation of large volume of acidic waste water. Therefore, the number of studies on heterogeneous catalysis in relation to biodiesel production is steadily increasing to address these problems [8], [9], [10], [11]. In heterogeneous catalysis process, some of the catalyst can be easily recovered from the crude biodiesel product and recycled to the process [11], [12], [13]. Furthermore, equipment corrosion can be prevented. Many heterogeneous catalysts, such as modified silica [14], modified strontium oxides [15], calcium zincate [16], calcium oxide [17], Ca/Al oxide-based alkaline composite [18], and Nafion [19] for biodiesel production from vegetable oils have been investigated. However, there are some factors that restrict the use of these catalysts, such as complexity in preparation, high cost, and unstable activity of catalysts [20].

Considering the environmental safety and cost of ion-exchange resin, it has some advantage compared with other heterogeneous catalysts [21]. In general, ion-exchange resins are made of a cross-linked polymeric matrix on which the active sites for the transesterification reaction are bonded [22], [23]. In addition, compared with other heterogeneous catalysts, ion-exchange resin can be easily separated from crude biodiesel because of its relatively large particle diameter (0.5–1.5 mm). In 2012, Li et al. [24] produced biodiesel from yellow horn (Xanthoceras sorbifolia Bunge) seed oil using a high alkaline anion-exchange resin, wherein a high conversion yield of about 96% was achieved. However, anion-exchange resins are suitable only for slightly acidic raw materials, such as the yellow horn (X. sorbifolia Bunge), which has an acid value of 0.5–0.7 mg KOH/g. Furthermore, an alkaline resin is not suitable for waste cooking oil with high acid value. Feng et al. [25] used a cation-exchange resin as heterogeneous catalyst to produce biodiesel from waste frying oils, wherein the maximal conversion of reaction achieved was approximately 90.0%. The low conversion rate may be attributed to lower acidity level of the catalyst which indicates the presence of Bronsted acid catalytic site. Thus, it is especially important to generate Lewis acid catalytic site instead of the Bronsted acid site to enhance the acidity of catalyst, and eventually improve the efficiency of conversion. In the present study, FeCl₃-modified cation-exchange resin was used as the catalyst in the esterification of ammonium lactate with butanol, wherein the esterification yield was reported to reach 96% [26]. Currently, no study has been reported on the use of FeCl₃-modified cation-exchange resin for biodiesel production and on the mechanism of the catalytic action of modified resin in the conversion of waste cooking oil to biodiesel.

The use of FeCl₃ modified strong acid styrene type cation-exchange resin (FMR) as catalyst for biodiesel production was explored in this study. The weight of FeCl₃·6H₂O loaded onto the resin, weight of solvent, reaction temperature, and reaction time were the parameters investigated during the experiment. The modified and unmodified resins were characterised using NH₃-Fourier transform infrared spectroscopy (NH₃-FTIR), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) to verify the mechanism of transesterification catalysed by FeCl₃ modified strong acid styrene type cation-exchange resin. These results can provide necessary data and theoretical support to the company, which uses ion-exchange resin as heterogeneous catalyst to produce biodiesel, and serve as an important theoretical foundation and basic data for the development and optimisation of biodiesel synthesis.

Section snippets

Materials

Waste cooking oil was obtained from the restaurant of the University of Science and Technology Beijing. Methanol (purity 99.8%), ethanol (purity 95%), Sodium methoxide were purchased from Sinopharm Chemical Reagent Co., Ltd. Pure methyl esters(ME), such as methyl palmitate, methyl oleate and other pure esters with purity of more than 99% were purchased from Beijing Century Aoke Biological Technology Co., Ltd.732ion exchange resins were purchased from Guangfu Chemical Research Institute

Modification of strong acid cation-exchange resin

As described in section 2.2, 30 g of modified hydrogen type macroporous styrene cation-exchange resin were mixed with FeCl₃·6H₂O and ethanol in a certain mass ratio, and reacted under a certain temperature to obtain modified resin. In general, a higher Fe load rate results to better catalysis. The reaction equation between hydrogen type cation-exchange resin and FeCl₃ was given in Eq. (4).

Based on the reaction presented in Eq. (4) and the exchange capacity (2.42 mmol/g) of strong acid groups in

Conclusion

(1)
The modification of ion-exchange resin using FeCl₃ was conducted, and the following optimum conditions were determined: FeCl₃·6H₂O dosage two times the resin weight (ratio of Fe actual weight to theoretical weight = 3.45:1), reaction temperature of 78 °C, reaction time of 3 h, and ethanol weight four times the resin weight. Finally, Fe load rate of resin reached 10.97%, which was 92.13% the theoretical load rate. Results of NH₃-FTIR, FTIR, and XRD showed that –OH of SO₃H group in modified resin

Acknowledgements

The project was supported by the National Environmental Protection Public Welfare Science and Technology Research Program of China (Project No. 201309023) and International cooperation project (2013DFG92600).

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Transesterification of waste cooking oil using FeCl3-modified resin catalyst and the research of catalytic mechanism

Highlights

Abstract

Introduction

Section snippets

Materials

Modification of strong acid cation-exchange resin

Conclusion

Acknowledgements

Energy

Energy

Energy

Energy

Bioresour. Technol.

Renew. Energy

Fuel

Chem. Eng. J.

Chem. Eng. Sci.

Energy

Fuel

Bioresour. Technol.

Fuel

Chem. Eng. J.

J. Catal.

Transesterification of waste cooking oil using FeCl₃-modified resin catalyst and the research of catalytic mechanism