Catalytic production of fused tetracyclic high-energy-density fuel with biomass-derived cyclopentanone and benzoquinone

doi:10.1016/S1872-2067(24)60148-8

Abstract

Abstract:

High-energy-density (HED) fuels (e.g. JP-10) are of great importance in safeguarding territorial air security, since they can increase the flight range and payload of military aircrafts. To reduce the reliance on limited petroleum source, the production of HED fuel with renewable biomass feedstocks is highly appealing. But currently, most of the synthetic biofuels, due to their intrinsic ring structure, are incapable of competing with JP-10 in terms of energy density and freezing point. By emulating the structural characteristic of JP-10, we herein design and prepare a special C₁₆ fused tetracyclic biofuel using renewable cyclopentanone and benzoquinone as feedstocks. Key to success depends on selective dehydration of vicinal diol (dimer of cyclopentanone) over Amberlyst-15 in [Hmim]Cl. The Amberlyst-15/[Hmim]Cl system effectively suppresses the dominant pinacol-type rearrangement pathway and also exhibits good reusability for the dehydration. The hydrogen-bonding interaction between vicinal diol and imidazolium ring, as well as electrostatic force between carbocation intermediate and chloride anion contribute to the high diene selectivity. The compact ring framework gives rise to a density of 0.966 g/mL, combustion heat of 43.1 MJ/L, freezing point of ‒67 °C, and kinematic viscosity of 12.4 cSt, which are comparable to the properties of JP-10. It is expected that this as-prepared HED biofuel may potentially serve as a renewable alternative to petroleum fuel JP-10.

Key words: High-energy-density fuel, Cyclopentanone, Dehydration reaction, Ionic liquid, Hydrogen bond, Biomass

Xu Zhang, Wen-Jing Zhang, Yan-Cheng Hu, Zhi-Guang Zhang, Jing-Pei Cao. Catalytic production of fused tetracyclic high-energy-density fuel with biomass-derived cyclopentanone and benzoquinone[J]. Chinese Journal of Catalysis, 2024, 67: 166-175.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60148-8

https://www.cjcatal.com/EN/Y2024/V67/I12/166

Figures/Tables 9

Table 1 The structure and property of typical petroleum-derived HED fuels.

Typical HED fuel	Density (g/mL)	Freezing point (°C)	Kinematic viscosity (cSt)	Combustion Heat (MJ/L)
JP-10	0.936	‒79	19 (‒40 °C)	39.6
RJ-4	0.927	‒40	60 (‒40 °C)	39.0
RJ-5	1.080	0	—	44.9

Fig. 1. Catalytic production of high-energy-density fused tetracyclic jet fuel with biomass derivatives.

Fig. 2. Effects of reaction conditions on the catalytic dehydration of CPDIOL 2. (a) The yield of CPDE 3 and SK 3’ as a function of different solvent. (b) The yield of CPDE 3 and SK 3’ as a function of different ionic liquid. (c) The yield of CPDE 3 and SK 3’ as a function of different catalyst. (d) The yield of CPDE 3 and SK 3’ as a function of different temperature. Reaction conditions: CPDIOL 2 (0.5 g), solvent (2.0 g), catalyst (10 wt%), T °C, 6 h. (a) A-15 (10 wt%), 120 °C. (b) A-15 (10 wt%), 120 °C. (c) [Hmim]Cl (2.0 g), 120 °C. (d) A-15 (10 wt%), [Hmim]Cl (2.0 g).

Fig. 3. The effect of catalyst dosage and recycling experiment of A-15/[Hmim]Cl. (a) The yield of CPDE 3 and SK 3’ as a function of catalyst dosage. (b) Reusability of A-15/[Hmim]Cl. (c) 1H NMR of used [Hmim]Cl after six runs. (d) 13C NMR of used [Hmim]Cl after six runs. Reaction conditions: CPDIOL 2 (0.5 g), [Hmim]Cl (2.0 g), A-15, 110 °C, 6 h.

Fig. 4. The interaction between CPDIOL 2 and [Hmim]Cl. (a) 1H NMR spectra of CPDIOL, [Hmim]Cl and their mixtures. (b) 13C NMR spectra of CPDIOL, [Hmim]Cl and their mixtures. (c) FT-IR spectra of CPDIOL, [Hmim]Cl and their mixtures. (d) The dehydration selectivity in strong polar solvents as a function of dosage of LiCl additive.

Fig. 5. The mechanism for the dehydration of CPDIOL 2 to CPDE 3 over Amberlyst-15 in [Hmim]Cl.

Fig. 6. Catalytic hydrodeoxygenation of D-A adduct 5. (a) Effect of H-type zeolites on the hydrodeoxygenation of D-A adduct 5. (b) Effect of metal/carbon (M/C) and Raney metals on the hydrodeoxygenation of D-A adduct 5. (c) Effect of temperature on the hydrodeoxygenation of D-A adduct 5. (d) The yield of fused tetracyclic fuel 6 over Pd/C and H-Y as a function of recycling time. Reaction conditions: D-A adduct 5 (1.0 mmol, 242.0 mg), M/C (5% metal content) or Raney metal (20 wt%), H-type zeolite (20 wt%), H2 (3.5 MPa), cyclohexane (2 mL), 15 h. (a) Pd/C, 200 °C. (b) H-Y, 200 °C. (c) Pd/C, H-Y. (d) Pd/C, H-Y, 200 °C.

Fig. 7. A four-step renewable route for the production of C16 fused tetracyclic fuel 6.

Table 2 Properties of the synthesized biofuel and conventional petroleum-based HED fuels.

HED fuel	Density (g/mL)	Freezing point (°C)	Kinematic viscosity (cSt)	Combustion Heat (MJ/L)
Fuel 6	0.966	−67	12.4 (30 °C)	43.1
JP-10	0.936	−79	19 (−40 °C) 7.3 (30 °C)	39.6
RJ-4	0.927	−40	60 (−40 °C)	39.0

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