Full Length ArticleCatalytic synthesis of renewable hydrocarbons via hydrodeoxygenation of angelica lactone di/trimers
Introduction
The search for renewable source of energy has been intensified due to the uncertainty surrounding the global market of crude oil. Biomass especially lignocelluloses or agricultural residues could provide the needed energy for sustainable development if efficient conversion technologies are developed. In order to advance the field, Simonetti et al. [1] coupled cracking reactions with Fischer-Tropsch synthesis to produce liquid alkanes from biomass-derived glycerol. Likewise, liquid hydrocarbons were produced through dehydration of sugars derived from biomass followed by aldol condensation and hydrogenation reactions [2]. Recent studies have revealed the possibility of producing more specific products from carbohydrates using modified catalytic systems. One-pot conversion of sugar to n-alkane without C–C dissociation over Ir-ReOx/SiO2 catalyst with co-catalyst H-ZSM-5 was reported by the research group of Keiichi Tomishige and high yields of n-hexane and n-pentane were obtained at 413–443 K after 72 h [3]. Subsequently, Beeck et al. [4] investigated the direct catalytic conversion of cellulose to liquid straight-chain alkanes in the presence of tungstosilicic acid and modified Ru/C. Under the optimized conditions, 82% yield of n-hexane was obtained with little amounts of gaseous and char products. Owing to the volatility of n-hexane and n-pentane, their uses as renewable transportation fuels are limited and therefore alternative route for the production of larger alkanes are required.
Conversion of biomass-derived carbohydrates into a suitable liquid fuel requires the formation of C–C bonds between the carbon chains [5], [6]. Carbon–Carbon coupling by aldol condensation reactions, ketonization processes and hydroalkylation/alkylation reactions are being carried out on biomass-derived platform molecules to produce suitable fuels for automobile applications [5], [7], [8]. Aldol-condensation of biomass-derived cyclopentanone and butanal followed by hydrodeoxygenation (HDO) reaction produced jet-fuel range cycloalkanes [9]. The condensation reaction was catalysed by magnesium-aluminum hydrotalcite (MgAl-HT) while the HDO reaction was performed over Ni/SiO2, Pd/SiO2 or bimetallic Ni-Pd/SiO2 catalyst. In a similar study, Sacia et al. [10] carried out a selective condensation of methyl ketones followed by HDO for the synthesis of aviation fuel. This strategy produced organic fractions containing mixtures of C12–C21 branched, cyclic alkanes, which were predicted to have a boiling point distribution similar to the distillation curve of traditional jet fuel [10]. Suojiang Zhang and co-workers used a novel approach to obtain highly branched alkanes rich in trimethylpentane using gamma-valerolactone as the starting material and the product has Research Octane Number (RON) of 95.4 which is similar to the RON of conventional gasoline [11].
In recent studies, angelica lactone commonly produced from levulinic acid in high yield can be constructed to form dimers and trimers, which upon HDO over suitable bifunctional catalysts yield organic fractions suitable for gasoline applications [12], [13], [14]. However, HDO of the constructed angelica lactone di/trimers was performed in the presence of noble metal catalysts [12], [13], [14], [15]. Here, we report the synthesis of Ni/ZSM-5 with Si/Al ratios of 40 and 300 by wetness impregnation, while Ni/Ac-HPA (Ni incorporated onto phosphotungstic acid functionalized activated carbon) was prepared by sol-gel and wet impregnation techniques. The HDO activities of the catalysts were evaluated under different reaction conditions and products distribution revealed considerable amounts of hydrocarbon suitable for gasoline applications were produced.
Section snippets
Synthesis of Ni/ZSM-5
7 wt% Ni/ZSM-5 catalyst was prepared by wetness impregnation method [16]. 40 g of ZSM-5 (Si/Al: 40; 300) was dried at 120 °C for 24 h. Ni(NO3)2·6H2O (19.4 g) was dissolved in 60 mL of H2O and was slowly dropped onto ZSM-5 (1.5 mL per gram of support). The mixture was continuously stirred at room temperature for 15 min, sonicated for 30 min and then air-dried at 80 °C and further dried in vacuum at 120 °C for 6 h. The prepared catalysts were initially calcined at 500 °C for 5 h and then reduced
Characterisation of hydrodeoxygenation catalysts
Protonation of the carbonyl group of oxygenated hydrocarbons easily occurred on an acidic support [20], therefore supports with acidic properties were utilised in this work. Table 1 showed the acidity of the catalysts. It is expected that catalyst prepared from ZSM-5 with SiO2/Al2O3 ratio of 40 would have higher acidity than the catalyst derived from ZSM-5 with SiO2/Al2O3 ratio of 300 since acidity of a zeolite is directly related to its aluminum content [21]. The acid density of ZSM-5
Conclusion
This study has provided insights into the HDO activities of Ni/ZSM-5 and Ni/Ac-HPA catalysts using biomass-derived angelica lactone di/trimers as renewable feedstock. The catalysts prepared through wetness impregnation methods were applied for the first time to convert angelica lactone di/trimers to transportation fuels. Chemical characterization of the catalysts revealed that the Ni metals were highly dispersed and readily reduced to its metal form, making them active for HDO reactions. This
Acknowledgements
This work was supported by International S&T Cooperation Program of China (2014DFA61670), National Natural Science Foundation of China (Nos. 21576269, 21276260, 21210006) 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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