Research on KOH/La-Ba-Al2O3 catalysts for biodiesel production via transesterification from microalgae oil

doi:10.1016/S1003-9953(11)60431-3

Journal of Natural Gas Chemistry

Volume 21, Issue 6, November 2012, Pages 774-779

https://doi.org/10.1016/S1003-9953(11)60431-3 Get rights and content

Abstract

Alumina supports modified by lanthanum (La) and barium (Ba) were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various techniques, including N₂ adsorption-desorption (Brunauer-Emmet-Teller method, BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and fourier transform infrared absorption spectroscopy (FT-IR). Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC. BET results showed that the support possessed high specific surface area, suitable pore volume and pore size distribution. Activity results indicated that the catalyst with 25 wt% KOH showed the best activity for microalgae oil conversion. XRD and SEM results revealed that Al–O–K compound was the active phase for microalgae oil conversion. The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.

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Citation Excerpt :
No KOH or K2O diffraction peaks were observed. This could be explained by the high dispersion of the active phase on the fumed silica support [17,27] and/or the presence of amorphous K2O species [3]. The calcination temperature utilized in this study (500 °C) is enough to allow the thermal decomposition of KOH to K2O.
In this study, several KOH loadings (10, 20, and 30 wt %) were impregnated on fumed silica (FS) using the wet impregnation method followed by calcination at 500 °C for 3 h. The catalysts were characterized by N₂ adsorption-desorption, X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR) techniques. Catalysts were tested in the transesterification of sunflower oil. The catalyst with a 30 wt % loading of KOH (30KOH/FS) showed the best catalytic performance by exhibiting the highest FAME yield. Optimum conditions for biodiesel production over this catalyst were, a reaction time of 4 h at 60 °C, a catalyst to oil ratio of 10 wt % and a methanol to oil molar ratio of 12:1 giving a final FAME yield of 99.9 %. The reusability study revealed a slight deactivation after 3 consecutive runs, attributed to the adsorption of hydrocarbons on the active sites. A breakthrough was achieved when the catalyst was coated with biodiesel (3 wt % with respect to oil in the initial methanol-oil mixture) which formed a protective layer over the active sites. This resulted in a better stability of the 30KOH/FS catalyst as it maintained the maximum FAME yield (99.9 %) over 3 consecutive runs. The properties of the produced biodiesel complied with the ASTM requirements. The coated catalyst also attained and maintained the maximum FAME yield (99.9 %) over 3 consecutive runs in the transesterification of waste cooking oil demonstrating its potential for industrial application.
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However, there is a concern about bonding between sulfate groups whereby metal cations causing insufficient reusability have been observed [31,32]. Aluminum is an element with high availability, suitable price, high thermal stability and surface area, and large pore size which can make good bonding with other oxides or active phases such as sulfate and is the most popular support of solid basic catalysts [33–35]. Al cations in the form of oxide have been used for improving the activity of SO4/Mg-Fe3O4 [36] and SO4/Fe-TiO2 [37] nanocatalysts for biodiesel production from waste cooking oil (WCO).
In this study, wastewater was utilized as an inexpensive medium for cultivating microalgae for biodiesel production using SO₄²⁻/Fe₃O₄-Al₂O₃ as a magnetic nanocatalyst. Next, some parameters affecting the growth of microalgae in a non-sterile medium (municipal wastewater), catalyst activity (sulfate and ferric oxide concentrations), and biodiesel production (transesterification reaction conditions) were assessed. Regarding the weight of cultivated microalgae, the highest growth was obtained after 5 days. The results of the catalyst studies indicated the important role of the sulfate groups in the activity of the alumina with the highest activity obtained at 2 M concentration of sulfuric acid. These groups formed sulfated alumina structures as active phases causing enhanced surface area, acidity, and activity. Further, the addition of ferric oxide to alumina at Fe/Al ratio of 0.25 resulted in production of a catalyst with suitable activity and magnetic properties while the sample with Fe/Al ratio of 0.15 and 0.35 presented negligible magnetic properties and insufficient enhancement in the activity, respectively. Finally, a yield of 87.6% was obtained using the best magnetic nanoparticle under the optimum conditions of 120 °C, catalyst concentration of 8 wt%, 9 mL methanol/g microalgae, and 4 h of reaction time. The best sample also showed appropriate reusability such that its activity declined by around 14.2% after the fifth cycle of use.
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Bottlenecks on the development of biodiesel production could be eliminated using direct transesterification (DT). This review presents a comprehensive overview for DT from oleaginous seed crops (edible and non-edible), microalgal and fungal/yeast biomass. Effects of key operational parameters, affecting the yield of biodiesel, such as feedstock, feedstock processing technologies, feedstock water content, catalyst choice, temperature, co-solvent and reaction time are summarised and critically assessed. 15% and 68% of published data showed high fatty acid (FA) yields and FA to fatty acid methyl ester (FAME) conversion efficiencies, respectively. Highest fatty acid yielding feedstock were Jatropha and a novel non-edible Mediterranean crop, Cynara cardunculus, the microalgae Chlorella and Nannochloropsis, and the fungi/yeast Trichosporon oleaginosus, Rhodosporidium toruloides, Lipomyces starkeyi, Mortierella isbellina, and Pichia guilliermondi. For wet microalgal biomass, a preference for acid-catalysed direct transesterification was determined, while base-catalysed DT was more suitable for dry biomass, except for turbo-thin film-assisted DT of microalgal biomass. The data highlight that DT operational parameters and technologies need optimisation for feedstock and water content and outcomes may be strongly strain-dependent for microalgal feedstock. To bring commercial biodiesel potential of some high-yielding feedstock to reality, comprehensive life cycle – and techno-economic analyses are required for intensified and non-intensified DT processing, taking feedstock production and possibilities of biorefinery concepts into account whilst also focussing on those processing platforms that can esterify fatty acids in wet biomass.
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Rare earths in Thai monazite ore were separated by chemical process following purification by an ion exchange process technique. They were utilized as raw materials to synthesize solid catalysts for the production of biodiesel. The novel solid catalysts were prepared by the simple oxalic acid precipitation method. The prepared CeO₂, La₂O₃ and Nd₂O₃ catalysts were employed to catalyze transesterification of palm oil and methanol. They showed high catalytic activity with FAME content over 95%. The catalytic performance of the best available La₂O₃ catalyst was additionally investigated. It was found that the initial transesterification rate catalyzed by the synthesized La₂O₃ catalyst was three times higher than its commercial counterpart, which related to its basic strength, high crystallinity, large pore volume and great crystallite size. The highest FAME content of 95% was achieved within 45 min under the optimal conditions of 200 °C reaction temperature, 39 bar reaction pressure, 1:30 molar ratio of oil to methanol, 10 wt% catalyst loading and 600 rpm stirring rate. In addition, the novel La₂O₃ catalyst was observed to be stable even after four recycle runs with insignificant loss of catalytic activity.

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: This work was supported by the Institute of Chemical Materials Foundation of CAEP (No. 626010937).

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Research on KOH/La-Ba-Al2O3 catalysts for biodiesel production via transesterification from microalgae oil

Abstract

J Taiwan Inst Chem Eng

J Nat Gas Chem

Biotech Advances

Biom Bioen

J Taiwan Inst Chem Eng

Fuel Proces Technol

Appl Clay Sci

Renew Enery

Chin J Catal (Cuihua Xuebao)

J Nat Gas Chem

J Nat Gas Chem

Research on KOH/La-Ba-Al₂O₃ catalysts for biodiesel production via transesterification from microalgae oil