Synthesis of renewable high-density fuels using cyclopentanone derived from lignocellulose

Article abstract of DOI:10.1039/c3cc46588h

By the combination of solvent-free aldol condensation and one-step hydrodeoxygenation under mild reaction conditions, a high-density (0.866 g mL^-1) bicyclic C₁₀ hydrocarbon was synthesized in high overall yield (up to 80%) using cyclopentanone derived from lignocellulose. The Royal Society of Chemistry 2014.

Full text of DOI:10.1039/c3cc46588h

Showcasing research from Tao Zhang’s Laboratory/State Key
Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian China.
As featured in:
Synthesis of renewable high-density fuels using cyclopentanone
derived from lignocellulose
-1
High-density (0.866 g mL ) bicyclic C hydrocarbon was
10
synthesized at high overall yield (up to 80%) by the combination
of solvent-free aldol condensation of cyclopentanone
which can be derived from lignocellulose and the one-step
hydrodeoxygenation under mild reaction conditions.
See Ning Li, Tao Zhang et al.,
Chem. Commun., 2014, 50, 2572.
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Synthesis of renewable high-density fuels using
cyclopentanone derived from lignocellulose†
Cite this: Chem. Commun., 2014,
0, 2572
5
ab
a
ab
a
a
Jinfan Yang, Ning Li,* Guangyi Li, Wentao Wang, Aiqin Wang,
a
a
a
Received 28th August 2013,
Accepted 16th December 2013
Xiaodong Wang, Yu Cong and Tao Zhang*
DOI: 10.1039/c3cc46588h
www.rsc.org/chemcomm
By the combination of solvent-free aldol condensation and one-step need for real application, new routes for the synthesis of renew-
hydrodeoxygenation under mild reaction conditions, a high-density able high-density liquid fuels using cheap and abundant feed-
À1
(
0.866 g mL ) bicyclic C10 hydrocarbon was synthesized in high overall stocks should be developed.
11
yield (up to 80%) using cyclopentanone derived from lignocellulose.
Cyclopentanone is a selective hydrogenation product of furfural
which has been produced on an industrial scale by the hydrolysis–
Recently, with the increasing social concern about the energy and dehydration of the hemicellulose in agriculture wastes and forest
environmental problems, the catalytic conversion of biomass to residues. Meanwhile, cyclopentanone is also an important compo-
1
2
12
renewable fuels and chemicals has become a hot topic. Jet fuel, nent in bio-oil produced by the pyrolysis of biomass. Considering
one of the most in demand transport fuels, is mainly derived from its cyclic structure, it can be used as a potential feedstock for the
petroleum. Lignocellulose is the main component of agriculture waste synthesis of high-density polycyclic aviation fuel. In this work, high
3
and forest residues. Pioneered by the Dumesic group and Huber overall yield (B80%) of a bicyclic C10 hydrocarbon (i.e. bi(cyclo-
et al., the synthesis of jet fuel range alkanes using the lignocellulose pentane)) was obtained, for the first time, by the combination of
derived platform chemicals has drawn tremendous attention. The self-condensation of cyclopentanone and one-step hydrodeoxygena-
4
5
most widely studied renewable jet fuel so far is primarily composed of tion (HDO) under solvent-free conditions (Scheme 1). This liquid
À1 13
linear or branched chain alkanes. These alkanes have many advan- fuel has a high density (0.866 g mL
) and net heat of combustion
À1
À1 14
tages such as good thermal stability, excellent combustion efficiency, (42.6 MJ kg ; 37.0 MJ L ). Therefore, it can be used as a
etc. However, the low densities (B0.76 g mL ) of these renewable jet renewable high-density fuel or an additive to increase the volumetric
À1
fuels require them to be blended with conventional jet fuels to meet heating value of conventional bio-jet fuels. As another potential
6
specifications. Compared with chain alkanes, cyclic hydrocarbons application, the bi(cyclopentane) can also be blended into the bio-
7
(
especially the polycyclic hydrocarbons) have higher densities and diesel to increase its mileage per litre (or gallon).
7
volumetric heating values due to strong ring strain. To make up the
The solvent-free self-aldol condensation of cyclopentanone was
shortage of chain alkanes, renewable jet fuel range cyclic alkanes or carried out at 423 K over a series of solid base catalysts. The detailed
aromatic compounds should also be synthesized and added to the information on the aldol condensation is provided in the ESI.†
5a,8
bio-jet fuel in order to increase its density. On the other hand, the From the analysis of GC and NMR (see Fig. S1 and S2 in the ESI†),
substitution of petroleum-based high-density polycyclic hydrocarbon 2-cyclopentylidene-cyclopentanone (i.e. 1a in Scheme 1) was identi-
tactical fuels, such as JP-10 and RJ-5, with biomass derived chemicals fied as the main product. Fig. 1 shows the conversion of the cyclo-
9
also has great significance. In the recent work of the Harvey group
pentanone and the yield of 1a over a series of solid base catalysts.
10
À1
and Zou et al., liquid fuels with a density of 0.94 g mL have been Among them, the magnesium–aluminium hydrotalcite (MgAl-HT)
successfully developed by the dimerization of pinene followed by and lithium–aluminium hydrotalcite (LiAl-HT), which have been
3a,5f,15
hydrogenation. As pinene is obtained from some specific wood proved to be active for other base catalysed reactions,
exhi-
and plant, the resource of raw material is limited. To fulfil the bited the best catalytic performances in the self-aldol condensation
a
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian 116023, China. E-mail: lining@dicp.ac.cn,
taozhang@dicp.ac.cn; Fax: +86 411 84691570
b
Graduate University of Chinese Academy of Sciences, Beijing 10049, China
†
Electronic supplementary information (ESI) available: Experimental section,
Scheme 1 Synthetic route for preparation of high-density cycloalkane
HPLC chromatogram and NMR spectra. See DOI: 10.1039/c3cc46588h
using the cyclopentanone derived from lignocellulose.
2
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Fig. 1 Conversion of cyclopentanone (white bar) and carbon yield of 1a
(black bar) over different solid base catalysts. The reaction was performed
Fig. 2 CO
2
-TPD of the different solid base catalysts. (The detailed infor-
with 4.0 g of cyclopentanone and 0.4 g of the catalyst at 423 K for 8 h in a
batch reactor.
2
mation about the CO -TPD test is given in the ESI.†)
condensation reaction, which may be the reason for the lower
of cyclopentanone. The sequence of the activities of different activity of the MgO catalyst than that of KF/Al in the self-aldol
catalysts follows the order: MgAl-HT > LiAl-HT > CaO > CaO– condensation of cyclopentanone. From the results of NH -TPD (see
CeO > KF/Al
> MgO. Over the MgAl-HT catalyst with a Mg/Al Table 1), it was noticed that the hydrotalcite catalysts, which are
atomic ratio of 3, up to 86% yield of 1a was obtained after more active in the self-aldol condensation of cyclopentanone, also
reaction at 423 K for 8 h.
have a higher amount of acid sites per unit mass of the catalyst. This
To figure out the reason for the activity difference of various solid can be another reason for the higher activity of these catalysts. As
2 3
O
3
2
2 3
O
16
base catalysts, we characterized them by N -adsorption, CO -TPD suggested in the literature, the synergetic effect of base sites and
2
2
and NH -TPD. From Table 1, no evident relationship between the acid sites is favourable for the aldol condensation.
3
specific BET surface areas and the catalytic activities of various solid
As the final aim of this work, the direct HDO of 1a was investi-
base catalysts was observed in the self-aldol condensation of cyclo- gated over different catalysts under solvent-free conditions. The
pentanone. Therefore, we cannot attribute the activity difference of reaction was carried out in a fixed-bed continuous flow reactor
various catalysts to their surface areas. According to the CO
results, the sequence of the amount of base sites over various results shown in Fig. 3, an evident support effect was observed for
catalysts is MgAl-HT > LiAl-HT > CaO > CaO–CeO
> MgO > KF/ the HDO of 1a. Over the Pd catalysts loaded on basic and neutral
Al O (see Table 1). This sequence is basically consistent with the supports (Pd/MgO and Pd/AC), C10 oxygenates (i.e. 2-cyclopentyl-
2
2
-TPD under relatively mild conditions (503 K, 6 MPa H ). From the
2
2
3
sequence of their activity in the self-aldol condensation of cyclo- cyclopentanone and 2-cyclopentyl-cyclopentanol) were identified as
pentanone. There is only one exception: compared with MgO, KF/ the major products. In contrast, when Pd was loaded on acidic
Al
KF/Al
can be rationalized by the strength of base sites. As shown in Fig. 2,
the CO -TPD curve of MgO shows a broad peak from 363 K to 673 K.
This peak can be attributed to the weak base sites. For KF/Al
2
O
3
shows higher activity although the amount of base sites over supports (such as SiO
2 2 2 3
, SiO –Al O and H-BETA zeolite, zirconium
2 3
O
is slightly lower than that over MgO. This phenomenon phosphate (ZrP)), the main product observed was bi(cyclopentane).
2
2 3
O ,
another desorption peak at 786 K can be observed. This peak can be
assigned to the CO desorption from medium-strength base sites.
2
2 2
For the CaO, CaO–CeO and hydrotalcite catalysts, evident CO
desorption peaks at higher temperature (>873 K) were observed,
indicating that these catalysts possess stronger basicity. As we found
5f
in our recent work, a strong base site is the active centre for aldol
Table 1 Specific BET surface areas (SBET) and the amounts of base sites
and acid sites over different solid base catalysts
S
BET
Base sites
amount (mmol g
Acid sites
amount (mmol g )
2
À1
À1
À1
Catalyst
MgO
KF/Al O
2 3
CaO–CeO
CaO
(m g
)
)
56
215
8
18
242
241
0.09
0.08
0.13
0.14
0.18
0.21
0.02
0.05
0.06
0.03
0.26
0.38
Fig. 3 Carbon yields of bi(cyclopentane) (black bar), C
1 5
–C light alkanes
(
grey bar) and C10 oxygenates (white bar) over different catalysts. Reaction
2
conditions: 503 K, 6 MPa; 1.8 g of the catalyst; liquid feedstock 2-cyclo-
À1
LiAl-HT
MgAl-HT
pentylidene–cyclopentanone (i.e. 1a in Scheme 1) flow rate 0.04 mL min
;
À1
hydrogen flow rate: 120 mL min
.
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As shown in Table S1 (ESI†), the metal dispersion of Pd/SiO
Communication
2
cyclopentanone as a platform chemical. Further studies on the
(27.4%) is higher than that of Pd/C (12.2%) and Pd/MgO (6.2%), utilization of cyclopentanone in the synthesis of renewable fuels
which can be one reason for the higher activity of Pd/SiO in the with lower freezing points and higher densities are underway in
2
HDO of 1a. Moreover, it is noticed that the metal dispersions of our laboratory.
Pd/H-BETA and Pd/ZrP are evidently lower than that of Pd/C, but
This work was supported by Natural Science Foundation of
they also exhibited high activity in the HDO of 1a. From the China (No. 21106143; No. 21277140), 100-talent project of
activities of three representative catalysts at lower temperature Dalian Institute of Chemical Physics (DICP) and the Independent
(453 K) (see Fig. S3 in ESI†), higher yield of bi(cyclopentane) Innovation Foundation of State Key Laboratory of Catalysis
(
85%) can be obtained over Pd/H-BETA than over Pd/SiO (70%) (No. R201113) of DICP.
2
and Pd/C (6.8%). These results indicate that the acidity of the
support is also important in the HDO of 1a. According to the recent Notes and references
work of Li and Huber on the reaction mechanism for the HDO of
biomass derived oxygenates, the dehydration over acid sites
followed by the hydrogenation over metal sites is the major path-
1
2
(a) G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006, 106,
17
4
044–4098; (b) D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green
Chem., 2010, 12, 1493–1513.
(a) A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
2
way for the C–O cleavage. Over the Pd/SiO catalyst, high yield of
2
411–2502; (b) P. Gallezot, Chem. Soc. Rev., 2012, 41, 1538–1558;
bi(cyclopentane) (90%) was obtained. Such a yield is comparable
with what was achieved in the previous work of the Dumesic
(
c) X. Wang and R. Rinaldi, Energy Environ. Sci., 2012, 5, 8244–8260.
3 (a) G. W. Huber, J. N. Chheda, C. J. Barrett and J. A. Dumesic, Science,
2005, 308, 1446–1450; (b) J. Q. Bond, D. M. Alonso, D. Wang, R. M. West
and J. A. Dumesic, Science, 2010, 327, 1110–1114; (c) R. M. West,
Z. Y. Liu, M. Peter and J. A. Dumesic, ChemSusChem, 2008, 1, 417–424.
4 (a) R. Xing, A. V. Subrahmanyam, H. Olcay, W. Qi, G. P. van Walsum,
H. Pendse and G. W. Huber, Green Chem., 2010, 12, 1933–1946;
3a,c
5c,18
group (79–94%) and Corma et al.
(80–95%) on the synthesis
of furfural-based diesel or jet fuel range alkanes. According to the
1
3,14
À1
literature,
bi(cyclopentane) has a high density (0.866 g mL )
À1
À1
and net heat of combustion (42.6 MJ kg ; 37.0 MJ L ). Therefore,
we believe that it may be used as a promising high-density aviation
fuel or an additive to increase the volumetric heating value of bio-
jet fuel or bio-diesel. Considering the high price and low availability
of Pd, the exploration of non-noble metal HDO catalysts has great
significance in practical application. In a recent work of Lercher
(
b) H. Olcay, A. V. Subrahmanyam, R. Xing, J. Lajoie, J. A. Dumesic
and G. W. Huber, Energy Environ. Sci., 2013, 6, 205–216.
5 (a) C. Zhao, Y. Kou, A. A. Lemonidou, X. B. Li and J. A. Lercher,
Angew. Chem., Int. Ed., 2009, 48, 3987–3990; (b) B. G. Harvey and
R. L. Quintana, Energy Environ. Sci., 2010, 3, 352–357; (c) A. Corma,
O. de la Torre, M. Renz and N. Villandier, Angew. Chem., Int. Ed.,
2011, 50, 2375–2378; (d) P. Anbarasan, Z. C. Baer, S. Sreekumar,
E. Gross, J. B. Binder, H. W. Blanch, D. S. Clark and F. D. Toste,
Nature, 2012, 491, 235–239; (e) G. Li, N. Li, Z. Wang, C. Li, A. Wang,
X. Wang, Y. Cong and T. Zhang, ChemSusChem, 2012, 5, 1958–1966;
( f ) J. Yang, N. Li, G. Li, W. Wang, A. Wang, X. Wang, Y. Cong and
T. Zhang, ChemSusChem, 2013, 6, 1149–1152.
1
9
and Zhao et al., the Ni–SiO catalyst prepared by the deposition–
2
precipitation method was found to be active for the cleavage of
ether bonds of lignin-derived aromatic ethers and hydrogenation of
oxygen-containing intermediates at low temperatures. Enlightened
6
H. A. Meylemans, L. C. Baldwin and B. G. Harvey, Energy Fuels, 2012,
7, 883–888.
by this work, we believe that the Ni–SiO
promising HDO catalyst. To verify this hypothesis, we prepared the
Ni–SiO and Cu–SiO catalysts according to the method of Lercher
2
catalyst is probably also a
2
7 H. A. Meylemans, R. L. Quintana, B. R. Goldsmith and B. G. Harvey,
ChemSusChem, 2011, 4, 465–469.
2
19
2
8
9
C. Zhao, D. M. Camaioni and J. A. Lercher, J. Catal., 2012, 288, 92–103.
(a) B. G. Harvey, M. E. Wright and R. L. Quintana, Energy Fuels, 2009,
24, 267–273; (b) B. G. Harvey, M. E. Wright and R. L. Quintana,
Energy Fuels, 2010, 24, 267–273; (c) H. A. Meylemans, R. L. Quintana
and B. G. Harvey, Fuel, 2012, 97, 560–568.
et al., and studied the catalytic performances of these catalysts for
the HDO of 1a under the same conditions as used for Pd catalysts.
As we expected, both Ni–SiO and Cu–SiO catalysts exhibited good
2
2
catalytic performances for the HDO of 1a. Compared with Cu–SiO2,
10 J.-J. Zou, N. Chang, X. Zhang and L. Wang, ChemCatChem, 2012, 4,
higher bi(cyclopentane) yield (93%) can be obtained over Ni–SiO
This value is comparable with the yield of bi(cyclopentane) over the
Pd/SiO catalyst (90%) under the same reaction conditions. More-
over, the stability of the Ni–SiO catalyst was also studied. From
Fig. S4 (ESI†), no evident decrease of catalytic performance over
2
.
1289–1297.
1
1 (a) M. Hronec and K. Fulajtarova, Catal. Commun., 2012, 24,
00–104; (b) M. Hronec, K. Fulajtarova and T. Liptaj, Appl. Catal.,
1
2
A, 2012, 437, 104–111; (c) Y. Yang, Z. Du, Y. Huang, F. Lu, F. Wang,
J. Gao and J. Xu, Green Chem., 2013, 15, 1932–1940.
2 (a) A. Demirbas, Fuel Process. Technol., 2007, 88, 591–597; (b) M. F.
Demirbas, Energy Sources, Part A, 2006, 28, 1181–1188.
13 (a) R. Y. Levina, V. R. Skvarchenko and O. Y. Okhlobystin, Zh. Obshch.
Khim., 1955, 25, 1466–1469; (b) M. B. Turovapolyak, I. E. Sosnina and
E. G. Treshchova, Zh. Obshch. Khim., 1953, 23, 1111–1116.
2
1
Ni–SiO was observed during a 24 hours continuous test, indicating
2
that this catalyst is very stable under the investigated conditions.
According to the ICP analysis of the HDO product, and fresh and
used catalysts (see Table S2 in ESI†), no leaching of Ni or Cu was
1
4 M. H. Gollis, L. I. Belenyessy, B. J. Gudzinowicz, S. D. Koch, J. O.
Smith and R. J. Wineman, J. Chem. Eng. Data, 1962, 7, 311–316.
observed during the HDO of 1a. Taking into consideration the 15 (a) G. S. Macala, A. W. Robertson, C. L. Johnson, Z. B. Day, R. S. Lewis,
M. G. White, A. V. Iretskii and P. C. Ford, Catal. Lett., 2008, 122,
2
excellent performance and good stability of the Ni–SiO catalyst, we
believe it is a promising catalyst for future applications.
2
05–209; (b) G. S. Macala, T. D. Matson, C. L. Johnson, R. S. Lewis,
A. V. Iretskii and P. C. Ford, ChemSusChem, 2009, 2, 215–217.
In summary, the solvent-free self-aldol condensation of cyclo- 16 (a) M. a. J. Climent, A. Corma, S. Iborra and A. Velty, J. Mol. Catal. A:
Chem., 2002, 182–183, 327–342; (b) W. Q. Shen, G. A. Tompsett,
R. Xing, W. C. Conner and G. W. Huber, J. Catal., 2012, 286,
pentanone followed by hydrodeoxygenation (HDO) is a promising
way for the production of renewable high density aviation fuel or
248–259.
diesel. Compared with the route described in the literature, the 17 N. Li and G. W. Huber, J. Catal., 2010, 270, 48–59.
1
8 A. Corma, O. de la Torre and M. Renz, Energy Environ. Sci., 2012, 5,
328–6344.
new protocol has obvious advantages of a lower price and higher
availability of feedstock. This work provides a new general
strategy for the synthesis of high-density jet fuel or diesel with
6
19 J. Y. He, C. Zhao and J. A. Lercher, J. Am. Chem. Soc., 2012, 134,
20768–20775.
2
574 | Chem. Commun., 2014, 50, 2572--2574
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