Hydrodeoxygenation of angelica lactone dimers and trimers over silica-alumina supported nickel catalyst
Introduction
The uncertainties surrounding fossil fuel have necessitated research into alternative sources such as nuclear power, hydropower, and lignocellulosic biomass [1]. However, lignocellulosic biomass has been recognized as the only source of renewable fuel [2].
Lignocellulosic materials can be converted into a versatile organic compound, levulinic acid (LA; 4-oxopentanoic acid) via acid hydrolysis [3]. LA could be produced from microcrystalline cellulose (MCC), cotton, cornstalk, fructose, glucose and starch in the presence of a mineral acid, HCl with concomitant production of equimolar amount of formic acid [4]. Hydrogenation of levulinic acid produces γ-valerolactone, GVL, which can be used as a blending agent (10% v/v) in conventional gasoline [5] or as a co-solvent in splash blendable diesel fuel [6]. Alternatively, GVL can undergo decarboxylation to produce butene in the presence of an acid catalyst (e.g. SiO2/Al2O3). The butene produced can then be passed into the oligomerization reactor in the presence of Amberlyst or ZSM-5 to produce larger alkenes suitable as transportation fuels [7]. Xin and co-workers [8] also reported the production of high octane number gasoline from GVL. Recently, a range of linear alkanes suitable for use as transportation fuels has been produced from biomass of diverse functional groups [9]. Their approach was based on organocatalyzed aldol condensation of isolable furfuraldehyde-based derivatives under mild conditions to produce only linear alkanes with n ≥ 9. However, most of the reports on C–C coupling reactions are carried out in the presence of organic solvent leading to difficulties in products separation.
Recently, our research groups discovered solvent-free C–C formation between angelica lactones (4-Hydroxy-3-pentenoic acid γ-lactone). Angelica lactones (ALs) could be produced by acid-dehydration of LA which itself could be derived from renewable source. Although ALs does not undergo aldol–condensation reaction to form ring structures of appropriate molecular weight for liquid fuel production because it does not possess an α-H atom. Alternatively, angelica lactone can undergo di/trimerization reaction to give a product with increased number of carbon atoms. This process was catalyzed by K2CO3 and the reaction completed within a short time (∼5 min) [4]. The dimer and trimer produced were then hydrogenated over expensive metal catalyst (Pd/C) to mainly C6–C12 alkanes and aromatics. Thus, we have extended our studies on the use of cheap heterogeneous catalyst (Ni/SiO2–Al2O3) for the production of bioalkanes and aromatics suitable for gasoline application through hydrodeoxygenation of angelica lactone dimer and trimer. The process yields organic stream which spontaneously separates from the aqueous phase. With the appropriate mix of reaction conditions such as hydrogen pressure, temperature and time; liquid products suitable for transportation fuels was obtained.
Section snippets
Materials and methods
α-angelica lactone (reagent grade) was supplied by Wuhan Chi-Fei Chemical Co. and used without further purification. K2CO3 (purity 99.0%) and acetone (purity 99.5%) were provided by Beijing Chemical Works, China. The commercial catalyst, nickel on silica-alumina (B.E.T surface area = 181.498 m2/g) was obtained from Alfa Aesar, China.
Di/trimerization of α-angelica lactone was carried out in a batch reactor heated with the aid of thermostatically controlled oil bath (±273 K). Initially, 3 g of K2
Di/trimerization reaction
α-angelica lactone (molecular weight; 98.10 g mol−1) can be constructed to yield higher molecular weighted compound by coupling of C–C bonds in the presence of K2CO3 [4].
The produced di/trimers contain 10–15 carbon numbers which are within a suitable range for biogasoline production. Building C–C linkages directly from smaller molecules to form larger molecules are of great importance in renewable energy parlance. Dumesic and his co-workers employed aldol–condensation reaction in building C–C
Conclusions
Renewable hydrocarbon fuel was produced through hydrodeoxygenation of angelica lactone di/trimers. The reaction was catalyzed by Ni/SiO2–Al2O3 and the effect of reaction conditions on the product distributions was investigated. At the optimized condition, conversion of angelica lactone dimer and trimer to bioalkanes reached 95%. Therefore, the hydrodeoxygenation process could be controlled to produce admixture of highly branched alkanes, aromatics and low amount of oxygenated hydrocarbons thus
Conflict of interest
We declare there is no conflict of interest whatsoever.
Acknowledgments
This work was supported by International S&T Cooperation Program of China (2014DFA61670), National Natural Science Foundation of China (Nos. 21276260, 21576269, 21476245) and External Cooperation Program of BIC, Chinese Academy of Sciences (No. GJHZ201306). We are thankful to The World Academy of Sciences (TWAS) and Chinese Academy of Sciences (CAS) for awarding a postgraduate fellowship to O.O.A.
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C hydrogenolysis.
O hydrogenation can be achieved.