Page 7 of 9
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
The Pt/Al2O3 and Pt/ZSM-22 showed typical catalytic unique hydroxyl group in fatty acid chain induced special thermal
performance when compared with other existing reports.32 When rearrangement reaction. Catalytic reactionDwOaIs: 1d0e.1s0i3g9n/eCd6GbCa0se0d94o2nE
non-hydroxyl oleic acid methyl ester was used as feedstock, the the thermal cracking products for jet fuel production. The methyl
main products over Pt/Al2O3 and Pt/ZSM-22 were n-C18 and C18 10-undecenoate was converted into branched paraffin with limited
(i/n being 4.2) paraffins when the reaction temperature was 360 °C, carbon loss over Pt/ZSM-22 catalyst. Another product, heptanal,
respectively.
was also converted into jet fuel through selective dimerization and
The catalytic performances of Pt/Al2O3 and Pt/ZSM-22 in methyl hydrodeoxygenation with supported amine and commercial
10-undecenoate hydrogenation are shown in Figure 8. The reaction available Pt/Al2O3 catalyst, respectively. The proposed process was
temperature largely influenced on both deoxygenation degree and used for the synthesis of jet fuel started from methyl 10-
i/n ratio. The deoxygenation was complete over both Pt/Al2O3 and undecenoate and heptanal obtained from thermal cracking of castor
Pt/ZSM-22 when reaction temperature was higher than 300 °C. The oil derived ricinoleic acid methyl ester. With the right integration of
i/n ratio over the investigated temperature range was very low these technologies, the carbon selectivity in castor oil to jet fuel
(below 0.1) over Pt/Al2O3 catalyst. Medium to high i/n ratio (~3) was process as high as 90%. The jet fuel products satisfied the jet-A
found when Pt/ZSM-22 was used as catalyst under different specification very well except for density.
reaction temperature. It was found that the Pt/ZSM-22 is stable
based on the characterization of the elemental and surface
properties of the used catalyst. The ICP analysis indicated there is
Reference
no Pt leaching during the hydrodeoxygenation reaction. Further XPS 1. J. Q. Bond, A. A. Upadhye, H. Olcay, G. A. Tompsett, J. Jae, R.
analysis (Figure 9) suggested that the Pt/ZSM-22 retained its zero
Xing, D. M. Alonso, D. Wang, T. Y. Zhang, R. Kumar, A. Foster, S.
M. Sen, C. T. Maravelias, R. Malina, S. R. H. Barrett, R. Lobo, C. E.
Wyman, J. A. Dumesic and G. W. Huber, Energy Environ. Sci.,
2014, 7, 1500-1523.
valent after reaction.33
3.5 Quality assessment of jet fuel produced from the proposed
technology
2. S. Karatzos, J. D. Mcmillan and J. N. Saddler, IEA Bioenergy Task
39, 2014, T39-T1.
The proposed process was used for the synthesis of jet fuel
started from methyl 10-undecenoate and heptanal obtained from
thermal cracking of castor oil derived ricinoleic acid methyl ester.
For conceptual proof purpose, the batch reactor which is better
defined with diamine supported Si-Al catalyst was used for heptanal
dimerization at 170 °C for 12 h. The product from dimerization
reaction and methyl 10-undecenoate were then hydro-processed
over Pt/Al2O3 (250 °C, 3 MPa) and Pt/ZSM-22 (300 °C, 4 MPa),
respectively. The carbon yield of the overall process was
approximately 90%. The products were tested as jet fuel, and the
values of some index detection are shown in Table 4. The total acid
number, flash point and freezing point of the product jet fuel are 0
mg KOH/g, 41 °C and -62 °C, respectively. The only exception of the
jet fuel product from the specification is the density (751 kg/m3),
which is slightly lower than the required value. However, this is the
common issue in iso-paraffin rich bio-jet fuel, which can be satisfied
by blending with aromatic containing petroleum derived jet fuel or
aromatic rich bio-jet fuel components.
3. K. Kandel, J. W. Anderegg, N. C. Nelson, U. Chaudhary and I. I.
Slowing, J. Catal., 2014, 314, 142-148.
4. B. X. Peng, Y. Yao, C. Zhao and J. A. Lercher, Angew. Chem. Int.
Ed., 2012, 51, 2072-2075.
5. P. Mäki-Arvela, M. Snåre, K. Eränen, J. Myllyoja and D. Y. Murzin,
Fuel, 2008, 87, 3543-3549.
6. S. Gopal, W. M. Zhang and P. G. Smirniotis, Ind. Eng. Chem. Res.,
2004, 43, 2950-2956.
7. M. Rabaev, M. V. Landau, R. Vidruk-Nehemya, V. Koukouliev, R.
Zarchin and M. Herskowitz, Fuel, 2015, 161, 287-294.
8. T. Li, J. Cheng, R. Huang, J. H. Zhou and K. Cen, Bioresour.
Technol., 2015, 197, 289-294.
9. C. X. Wang, Z. J. Tian, L. Wang, R. S. Xu, Q. H. Liu, W. Qu, H. J. Ma
and B. C. Wang, ChemSusChem, 2012, 5, 1974-1983.
10. D. Verma, R. Kumar, B. S. Rana and A. K. Sinha, Energy Environ.
Sci., 2011, 4, 1667-1671.
11. J. A. Martens, D. Verboekend, K. Thomas, G. Vanbutsele, J.
Gilson and J. Pérez-Ramírez, ChemSusChem, 2013, 6, 421-425.
12. M. Y. Kim, K. Lee and M. Choi, J. Catal., 2014, 319, 232-238.
13. B. Donnis, R. G. Egeberg, P. Blom and K. G. Knudsen, Top. Catal.,
2009, 52, 229-240.
4. Conclusion
Process for ricinoleic acid methyl ester conversion into jet fuel
14. S. Y. Liu, Q. Q. Zhu, Q. X. Guan, L. N. He and W. Li, Bioresour.
Technol., 2015, 183, 93-100.
with ultra-high carbon selectivity was designed and realized. The
15. V. Goldbach, P. Roesle, and Stefan Mecking, ACS Catal., 2015, 5,
5951-5972.
b
a
Pt 4f7/2
Pt 4f7/2
16. R. E. Murray, E. L. Walter, K. M. Doll, ACS Catal., 2014, 10, 3517-
3520.
Pt 4f5/2
Pt 4f5/2
17. K. Kandel, J. W. Anderegg, N. C. Nelson, U. Chaudhary, I. I.
Slowing, J. Catal., 2014, 314, 142-148.
18. S. Shylesh, D. Hanna, J. Gomes, C. G. Canlas, M. Head-Gordon,
A. T. Bell, ChemSusChem, 2014, 8, 466-472.
19. L. Faba, E. Díaz, S. Ordóñez, ChemSusChem, 2014, 7, 2816-2820.
20. Z. Wang, P. Fongarland, G. Z. Lu, N. Essayem, J. Catal., 2014, 318,
64
68
72
76
80
84
64
68
72
76
80
84
Binding Energy (eV)
Binding Energy (eV)
Figure 9 XPS spectra of Pt 4f in (a) Pt/ZSM-22 before reaction and (b) Pt/ZSM-22
after reaction.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins