Topics in Catalysis

, Volume 58, Issue 4–6, pp 350–358 | Cite as

One-Pot Catalytic Transformation of Dicyclopentadiene to High Energy Density Fuel Exo-tetrahydrotricyclopentadiene

  • Wentao Wang
  • Yu CongEmail author
  • Shuai Chen
  • Caixia Sun
  • Xiaodong Wang
  • Tao ZhangEmail author
Original Paper


Energy density of fuel is an important issue for advanced aircrafts and spacecrafts. Exo-tetrahydrotricyclopentadiene (exo-THTCPD) is a promising high-energy density fuel candidate with many desirable properties, including high volumetric energy content (43.2 MJ/L), high density (1.04 g/mL) and low freezing point (<−40 °C). In this work, we demonstrated the first example of one-pot catalytic synthesis of exo-THTCPD directly from dicyclopentadiene (DCPD). The whole procedure was fulfilled in one-pot by three steps. First, tricyclopentadiene (TCPD) was prepared directly from the dissociation–recombination of DCPD at 200 °C. Then the reaction mixture (the majority is TCPD, mixed with small amount of DCPD and tetracyclopentadiene) was saturated using supported noble metal catalysts at 150 °C under 4.0 MPa H2. Finally, the hydrogenated mixture was treated by AlCl3-catalytic isomerization at 15 °C. Like most synthesis processes, fractional distillation was needed to obtain the final product of exo-THTCPD. Compared with previous routes, the new protocol has many advantages such as one-pot, high concentration, less solvents, low catalyst loading, short reaction time, etc, and therefore showed great potential for industrial applications.

Graphical Abstract


High energy density fuel Tricyclopentadiene Hydrogenation Isomerization Exo-tetrahydrotricyclopentadiene 



The authors appreciate financial support by the National Natural Science Foundation of China (21202163). The authors gratefully acknowledge Guoliang Xu for fruitful discussion and Ting Lu for experimental assistance.

Supplementary material

11244_2015_376_MOESM1_ESM.docx (337 kb)
Supplementary material 1 (DOCX 337 kb)


  1. 1.
    Chung HS, Chen CSH, Kremer RA, Boulton JR (1999) Recent development in high-energy density liquid hydrocarbon. Energy Fuels 13:641–649CrossRefGoogle Scholar
  2. 2.
    Batonneau Y, Brahmi R, Cartoixa B, Farhat K, Kappenstein C, Keav S, Kharchafi-Farhat G, Pirault-Roy L, Saouabé M, Scharlemann C (2014) Green propulsion: catalysts for the european FP7 project GRASP. Top Catal 57:656–667CrossRefGoogle Scholar
  3. 3.
    Antonova TN, Abramov IA, Feldblyum VS, Abramov IG, Danilova AS (2009) Catalytic hydrogenation of dicyclopentadiene to dicyclopentene in the liquid phase. Petr Chem 49:366–368CrossRefGoogle Scholar
  4. 4.
    Zou JJ, Xu Y, Zhang XW, Wang L (2012) Isomerization of endo-dicyclopentadiene using Al-grafted MCM-41. Appl Catal A Gen 421–422:79–85CrossRefGoogle Scholar
  5. 5.
    Sibi MG, Singh B, Kumar R, Pendem C, Sinha AK (2012) Single-step catalytic liquid-phase hydroconversion of DCPD into high energy density fuel exo-THDCPD. Green Chem 14:976–983CrossRefGoogle Scholar
  6. 6.
    Wang W, Chen JG, Song LP, Liu ZT, Liu ZW, Lv J, Xiao JL, Hao ZP (2013) One-step, continuous-flow, highly catalytic hydrogenation-isomerization of dicyclopentadiene to exo-tetrahydrodicyclopentadiene over Ni-supported catalysts for the production of high-energy-density fuel. Energy Fuels 27:6339–6347CrossRefGoogle Scholar
  7. 7.
    Wang L, Zou JJ, Zhang XW, Wang L (2012) Isomerization of tetrahydrodicyclopentadiene using ionic liquid: green alternative for Jet Propellant-10 and adamantane. Fuel 91:164–169CrossRefGoogle Scholar
  8. 8.
    Marchand AP, Allen RW (1974) An improved synthesis of pentacyclo [,6.03,10.05,9] undecane. J Org Chem 39:1596CrossRefGoogle Scholar
  9. 9.
    Marchand AP (1989) Synthesis and chemistry of homocubanes, bishomocubanes, and trishomocubanes. Chem Rev 89:1011–1033CrossRefGoogle Scholar
  10. 10.
    Chang HO, Dai IP, Joong HR, Jeong SH (2007) Syntheses and characterization of cyclopropane-fused hydrocarbons as new high energetic materials. Bull Korean Chem Soc 28:322–324CrossRefGoogle Scholar
  11. 11.
    Kokan TS, Olds JR, Seitzman JM, Ludovice PJ (2008) Characterizing high-energy-density propellants for space propulsion applications. J Thermophys Heat Transfer 22:727–740CrossRefGoogle Scholar
  12. 12.
    Osmont A, Catoire L, Gokalp I (2008) Physicochemical properties and thermochemistry of propellanes. Energy Fuels 22:2241–2257CrossRefGoogle Scholar
  13. 13.
    Nguyen MD, Nguyen LV, Jeon EH, Kim JH, Cheong M, Kim HS, Lee JS (2008) Fe-containing ionic liquids as catalysts for the dimerization of bicycle[2.2.1]heap-2,5-diene. J Catal 258:5–13CrossRefGoogle Scholar
  14. 14.
    Wang L, Zou JJ, Zhang XW, Wang L (2011) Rearrangement of tetrahydrotricyclopentadiene using acidic ionic liquid: synthesis of diamondoid fuel. Energy Fuels 25:1342–1347CrossRefGoogle Scholar
  15. 15.
    Burdette GW, Schneider AI (1983) Exo-terahydrotricyclopentadiene, a high density liquid fuel. U.S. Patent No. 4401837Google Scholar
  16. 16.
    Wang L, Zhang XW, Zou JJ, Han H, Li YH, Wang L (2009) Acid-catalyzed isomerization of tetrahydrotricyclopentadiene: synthesis of high-energy-density liquid fuel. Energy Fuels 23:2383–2388CrossRefGoogle Scholar
  17. 17.
    Kim SG, Han J, Jeon JK, Yim JH (2014) Ionic liquid-catalyzed isomerization of tetrahydrotricyclopentadiene using various chloroaluminate complexes. Fuel 137:109–114CrossRefGoogle Scholar
  18. 18.
    Zhang XW, Jiang Q, Xiong ZQ, Zou JJ, Wang L, Mi ZT (2008) Diels-Alder addition of dicyclopentadiene with cyclopentadiene in polar solvents. Chem Res Chin Univ 24:175–179CrossRefGoogle Scholar
  19. 19.
    Li YH, Zou JJ, Zhang XW, Wang L, Mi ZT (2010) Product distribution of tricyclopentadiene from cycloaddition of dicyclopentadiene and cyclopentadiene: a theoretical and experimental study. Fuel 89:2522–2527CrossRefGoogle Scholar
  20. 20.
    Deng Q, Zhang XW, Wang L, Zou JJ (2014) Catalytic isomerization and oligomerization of endo-dicyclopentadiene using alkali-treated hierarchical porous HZSM-5. Chem Eng Sci. doi: 10.1016/j.ces.2014.08.060 Google Scholar
  21. 21.
    Zou JJ, Xiong ZQ, Wang L, Zhang XW, Mi ZT (2007) Preparation of Pd-B/Al2O3 amorphous catalyst for the hydrogenation of tricyclopentadiene. J Mol Catal A 271:209–215CrossRefGoogle Scholar
  22. 22.
    Zou JJ, Xiong ZQ, Zhang XW, Liu GZ, Wang L, Mi ZT (2007) Kinetics of tricyclopentadiene hydrogenation over Pd-B/γ-Al2O3 amorphous catalyst. Ind Eng Chem Res 46:4415–4420CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  1. 1.State Key Laboratory of CatalysisDalian Institute of Chemical Physics, Chinese Academy of SciencesDalianChina

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