Synthesis of renewable diesel with hydroxyacetone and 2-methyl-furan

Article abstract of DOI:10.1039/c3cc42296h

Diesel or jet fuel range branched alkanes were synthesized for the first time by the combination of hydroxyalkylation-alkylation (HAA) of 2-methylfuran with hydroxyacetone and subsequent hydrodeoxygenation. Due to the electron-withdrawing effect of the hy

Full text of DOI:10.1039/c3cc42296h

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Laboratory/State Key Laboratory of Catalysis,
Dalian Institute of Chemical Physics, Chinese Academy
of Sciences, Dalian, China
Synthesis of renewable diesel with hydroxyacetone and
2-methyl-furan
Diesel or jet fuel range branched alkanes were synthesized for the
first time by the combination of hydroxyalkylation–alkylation (HAA)
of 2-methylfuran with hydroxyacetone and hydrodeoxygenation.
Compared with the previous acetone route, hydroxyacetone route
exhibited higher HAA reactivity and diesel yield.
See Tao Zhang,
Chem. Commun., 2013, 49, 5727.
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Synthesis of renewable diesel with hydroxyacetone
and 2-methyl-furan†
Guangyi Li,ab Ning Li,a Shanshan Li,ab Aiqin Wang,a Yu Cong,a Xiaodong Wanga
and Tao Zhang*a
Cite this: Chem. Commun., 2013,
49, 5727
Received 29th March 2013,
Accepted 7th May 2013
DOI: 10.1039/c3cc42296h
www.rsc.org/chemcomm
Diesel or jet fuel range branched alkanes were synthesized for the first Dumesic’s group8 and Huber et al.,19 it was found that the aldol-
time by the combination of hydroxyalkylation–alkylation (HAA) of condensation of hydroxyacetone with furfural or 5-hydroxymethyl-
2-methylfuran with hydroxyacetone and subsequent hydrodeoxygena- furfural could take place under the catalysis of a solid base or organic
tion. Due to the electron-withdrawing effect of the hydroxyl group, base. However, due to the serious C–C cleavage, which occurred
the hydroxyacetone route exhibited evident advantages (higher HAA during the HDO of aldol condensation products, low yields of liquid
reactivity and diesel yield) over the previous acetone route.
alkanes (o30%) were obtained. To fulfill the need for real application,
some new routes with higher selectivity to diesel or jet fuel range
The efficient utilization of biomass for the production of fuels and alkanes should be developed. In the recent work of Corma et al.13,20,21
chemicals is a solution to the excessive dependence of our society on and our group,22,23 it was found that diesel or jet fuel range branched
fossil energy and the environmental problems caused by the utiliza- alkanes could be synthesized by the hydroxyalkylation–alkylation
tion of fossil fuels. In recent years, alkyl-fatty ester or biodiesel has (HAA) of 2-methylfuran (2-MF) with lignocellulose derived carbonyl
been used as an important alternative fuel due to its renewability, low compounds followed by the HDO. 2-MF can be prepared by the
toxicity, low sulphur content, high biodegradability and cetane selective hydrogenation of furfural which has been produced for
value.1–4 Glycerol is the by-product of biodiesel production. The decades on an industrial scale by the hydrolysis–dehydration of the
production of every 10 tons of biodiesel will lead to the generation hemicellulose part of agricultural waste and forest residues.24
of approximately one ton of glycerol. With the rapid growth of annual The lignocellulose derived carbonyl compounds can be aldehydes
biodiesel production from o1 million tons in 2000 to about 10 million (such as furfural, 5-hydroxymethylfurfural, methylfurfural, butanal
tons in 2010, a large quantity of glycerol was generated.5 The over- and ethanal), ketones (e.g. acetone and 2-pentanone) and levulinic
supply of glycerol led to the sharp decrease in glycerol price from acid or esters. However, to the best of our knowledge, there is no report
1.2–2 USD kgꢀ1 to 0.4 USD kgꢀ1.6 From the point of view of atom on the HAA of furan compounds with hydroxyacetone, let alone the
economy, the utilization of excess glycerol as the feedstock for fuels use of the HAA product as the precursor for the synthesis of diesel or
and high value-added chemicals is of great significance.6,7
jet fuel range branched alkanes. In this work, the HAA of 2-MF and
Diesel and jet fuel are two kinds of most in demand fuels. hydroxyacetone over a series of solid acid catalysts is reported for the
These fuels are mainly obtained from petroleum currently. first time. The as prepared HAA product was hydrodeoxygenated over
Lignocellulose is the main component of agricultural waste and forest the Pd/C catalyst.
residues. Following the pioneering work of Dumesic’s group8–10 and
The HAA of 2-MF and hydroxyacetone was carried out over a
Huber et al.,11,12 the synthesis of diesel and jet fuel range alkanes from series of solid acid catalysts. From HPLC, NMR and HR-GC-MS (see
lignocellulose derived platform chemicals has attracted tremendous Fig. S1–S4, ESI†) analyses, 2,2-bis(5-methylfuran-2-yl)propan-1-ol (i.e.
attention.13–16 Hydroxyacetone is the dehydration product of 1b in Scheme 1) was identified as the main product. Small amount
glycerol.17,18 This compound has a similar structure to acetone and of 7-hydroxy-6-methyl-6-(5-methylfuran-2-yl)heptane-2,5-dione (i.e. 1c
can be used as a potential platform compound in the synthesis of in Scheme 1) was detected as the by-product. This compound was
renewable diesel or jet fuel by the combination of C–C coupling produced by the hydrolysis of 1b. Based on the above information,
reaction and hydrodeoxygenation (HDO).2 In the previous work of the reaction pathway for the HAA of 2-MF with hydroxyacetone is
proposed in Scheme 1. The absence of 2-(5-methylfuran-2-yl)-
a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
propane-1,2-diol (i.e. 1a in Scheme 1) in liquid products can be
Academy of Sciences, Dalian 116023, China. E-mail: taozhang@dicp.ac.cn;
explained by the much higher rate of the alkylation step than that of
Fax: +86 411 84691570
b Graduate University of Chinese Academy of Sciences, Beijing 10049, China
hydroxyalkylation.22
Fig. 1 shows the conversion of 2-MF and yields of 1b and 1c
over a series of solid acid catalysts. Among them, Nafion-212
† Electronic supplementary information (ESI) available: Experimental section,
NMR and mass spectra. See DOI: 10.1039/c3cc42296h
c
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Fig. 2 TON and TOF of 2-MF to 1b over different solid acid catalysts. Reaction
conditions: 338 K, 2 h; 3.28 g (40 mmol) 2-MF, 1.48 g (20 mmol) hydroxyacetone
(2-MF : hydroxyacetone molar ratio was 2 : 1), and 0.015 g catalyst.
Scheme 1 Reaction pathway for the HAA of 2-methylfuran (2-MF) with
hydroxyacetone.
catalyst. Strong acid is more active than medium acid and weak acid
for this reaction. Analogously, the activity sequence of Nafion resins,
Amberlyst resins and sulfated active carbon can also be rationalized
by their acid strength. According to the literature,25–27 Nafion is
a perfluorinated sulfonic acid resin that is often denoted as a
superacid. Amberlyst is a sulfonic-acid-functionalized cross-linked
polystyrene resin. However, sulfated active carbon is amorphous
carbon bearing SO3H, COOH and phenolic OH groups which
function as acid sites. In Nafion resins, the acid strength of the
SO3H group is enhanced by the presence of fluorine, which makes
its acid strength higher than that of Amberlyst resins and sulfated
active carbons. Consequently, Nafion resins have the highest activity
and efficiency for the HAA of 2-MF with hydroxyacetone.
The stability of Nafion-212 in the HAA of 2-MF with hydroxy-
Fig. 1 Conversion of 2-MF and the yields of 1b and 1c over different solid acid
catalysts. Reaction conditions: 338 K, 2 h; 3.28 g (40 mmol) 2-MF, 1.48 g (20 mmol) acetone was also studied. To exclude the influence of reaction
hydroxyacetone (2-MF : hydroxyacetone molar ratio was 2 : 1), and 0.15 g catalyst.
residues (including hydroxyalkylation and HAA products,
unreacted hydroxyacetone and 2-MF), the catalyst was washed
exhibited the highest activity for the HAA of 2-MF with hydroxy-
acetone. The advantage of Nafion-212 resin is more significant at
low catalyst loading (see Fig. S5, ESI†). According to the results
shown in Fig. 1 and Fig. S5 (ESI†), the activity sequence of the
different catalysts is Nafion-212 > Nafion-115 > Amberlyst-15 >
Amberlyst-36 > AC-SO3H > H-b > ZrP > H-USY > H-ZSM-5. As far as
the TON and TOF of 2-MF to 1b (deduced from the 1b yield in
Fig. S5 (ESI†) and the acid amount measured by the chemisorption
of NH3) are concerned, the Nafion resins also demonstrated an
evidently higher catalytic efficiency than other solid acid catalysts
(see Fig. 2).
To find out the intrinsic reason for the difference in activity
of various catalysts, we also compared the activities of H2SO4,
H3PO4, and CH3COOH (these acids were chosen to represent strong
acid, medium acid and weak acid respectively). To facilitate the
comparison, the H+ molar concentration and the total acid amounts
of three acid solutions were kept the same (5 mol Lꢀ1 and
0.75 mmol). According to the results shown in Fig. S6 (ESI†), the
sequence for the yield of 1b under the catalysis of different acids is
H2SO4 (33.0%) > H3PO4 (0.5%) > CH3COOH (0.0%). Such a
sequence is consistent with that of acid strength. According to this
result, the HAA of 2-MF is sensitive to the acid strength of the
thoroughly with methanol after each usage and dried at 353 K
for 1 h. From the result shown in Fig. S7 (ESI†), no evident
change in activity of Nafion-212 resin was observed even after
being repeatedly used six times. This result shows that the
Nafion-212 resin is very stable under the investigated conditions.
According to the high activity and stability of Nafion-212 resin, it
can be considered as a promising catalyst for real application.
Fig. S8–S10 (ESI†) illustrate the influence of catalyst loading,
reaction temperature and reaction time on the yields of 1b and 1c
over Nafion-212 resin. Under optimum conditions, 70.8% yield of
1b and 8.3% yield of 1c were obtained over 0.15 g Nafion-212 resin
after reacting at 338 K for 6 h. Both 1b and 1c can be used as
precursors for synthesis of renewable diesel or jet fuel.
In the previous work of Corma et al.16 and our group,22,23
5,50-(propane-2,2-diyl)bis(2-methylfuran) was prepared by the
HAA of 2-MF with acetone. In this work, the reactivity of
hydroxyacetone and acetone in the HAA of 2-MF was compared
at 323 K. Under the same reaction conditions, an evidently
higher yield of the HAA product (41.6% vs. 24.7%) can be
achieved over Nafion-212 resin when hydroxyacetone was used
to replace acetone as the carbonyl compound to react with 2-MF
(see Fig. S11, ESI†). This can be considered as an advantage of
c
5728 Chem. Commun., 2013, 49, 5727--5729
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activity and stability. Under solvent-free conditions, 79.1% yield
of HAA products was obtained over Nafion-212 resin. After the
HDO of the HAA products over the Pd/C catalyst, 79.5% carbon
yield for diesel or jet fuel range alkanes could be achieved.
Compared with the 2-MF–acetone route described in our
previous work, the hydroxyacetone route has many advantages
such as the higher HAA reactivity and higher carbon yield of
diesel or jet fuel range alkanes in the HDO process, which
can be explained by the electron-withdrawing effect of the
hydroxyl group.
This work was supported by the Natural Science Foundation
of China (no. 21106143), 100 talent project of the Dalian
Institute of Chemical Physics (DICP), and the Independent
Innovation Foundation of State Key Laboratory of Catalysis
(no. R201113) of DICP.
Fig. 3 Carbon yields of different alkanes from the hydrodeoxygenation (HDO)
of HAA products between 2-MF and acetone or hydroxyacetone over the Pd/C
catalyst. Reaction conditions: 1.8 g catalyst; 643 K; liquid feedstock flow rate:
0.04 mL minꢀ1; hydrogen flow rate: 120 mL minꢀ1. The diesel, gasoline and light
alkanes account for C9–C13, C5–C8 and C1–C4 alkanes respectively. The method
used for the calculation of carbon yield is described in the ESI.†
Notes and references
1 G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006, 106,
4044–4098.
2 D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem., 2010, 12,
1493–1513.
3 L. C. Meher, D. V. Sagar and S. N. Naik, Renewable Sustainable Energy
Rev., 2006, 10, 248–268.
4 F. R. Ma and M. A. Hanna, Bioresour. Technol., 1999, 70, 1–15.
5 C.-H. Zhou, J. N. Beltramini, Y.-X. Fan and G. Q. Lu, Chem. Soc. Rev.,
2008, 37, 527–549.
6 Y. Nakagawa and K. Tomishige, Catal. Sci. Technol., 2011, 1,
179–190.
7 C. H. C. Zhou, J. N. Beltramini, Y. X. Fan and G. Q. M. Lu, Chem. Soc.
Rev., 2008, 37, 527–549.
8 G. W. Huber, J. N. Chheda, C. J. Barrett and J. A. Dumesic, Science,
2005, 308, 1446–1450.
9 E. L. Kunkes, D. A. Simonetti, R. M. West, J. C. Serrano-Ruiz,
C. A. Gartner and J. A. Dumesic, Science, 2008, 322, 417–421.
10 J. Q. Bond, D. M. Alonso, D. Wang, R. M. West and J. A. Dumesic,
Science, 2010, 327, 1110–1114.
11 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.
12 H. Olcay, A. V. Subrahmanyam, R. Xing, J. Lajoie, J. A. Dumesic and
G. W. Huber, Energy Environ. Sci., 2013, 6, 205–216.
13 A. Corma, O. de la Torre, M. Renz and N. Villandier, Angew. Chem.,
Int. Ed., 2011, 50, 2375–2378.
the hydroxyacetone route. The higher reactivity of hydroxyacetone
can be explained by the enhanced electrophilicity of the carbonyl
group by the electron-withdrawing effect of the hydroxyl group
attached to one of the a-carbon atoms.
As the final aim of this work, the HDO of HAA products of 2-MF
and hydroxyacetone (with 1b as the main component) was also
explored over the Pd loaded active carbon catalyst. The results are
shown in Fig. 3. From GC-MS analysis, the HAA products of 2-MF
and hydroxyacetone were totally converted at 643 K, with CO2 and
hydrocarbons as the final products. This result shows that 643 K is
enough for the complete HDO of 1b and 1c. Compared with the
HDO of the HAA product of 2-MF with acetone under the same
reaction conditions, an evidently higher carbon yield for diesel or jet
fuel range alkanes (79.5% vs. 62.1%) and C13 alkanes (56.5% vs.
44.4%) can be obtained by the HDO of HAA products of 2-MF with
hydroxyacetone. The predominant component of the C13 alkanes
from the HDO of HAA products of 2-MF with hydroxyacetone is 2,2-
dimethyl-undecane. The higher carbon yield of diesel or jet fuel
range alkanes in the HDO of HAA products of 2-MF with hydroxy-
acetone can be also explained by the presence of the hydroxyl
group. In the previous work of Corma et al.21 and our group,23 it was
14 S. Crossley, J. Faria, M. Shen and D. E. Resasco, Science, 2010, 327,
68–72.
15 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.
16 B. G. Harvey and R. L. Quintana, Energy Environ. Sci., 2010, 3,
352–357.
found that C–C cleavage in the HDO of HAA products is preferable 17 S. S. Niu, Y. L. Zhu, H. Y. Zheng, W. Zhang and Y. W. Li, Chin. J.
Catal., 2011, 32, 345–351.
18 S. Sato, D. Sakai, F. Sato and Y. Yamada, Chem. Lett., 2012, 41,
at branched carbon atoms. Carbocations will be generated by C–C
cleavage which can decrease the diesel or jet fuel yield. The extent of
965–966.
C–C cleavage depends on the stability of carbocations formed 19 A. V. Subrahmanyam, S. Thayumanavan and G. W. Huber, Chem-
SusChem, 2010, 3, 1158–1161.
20 A. Corma, O. de la Torre and M. Renz, ChemSusChem, 2011, 4,
during the HDO process. In the HDO of HAA products of 2-MF
with acetone and hydroxyacetone, tertiary carbocations will be
1574–1577.
generated with the C–C cleavage at branched carbon atoms. Due 21 A. Corma, O. de la Torre and M. Renz, Energy Environ. Sci., 2012, 5,
6328–6344.
to the electron-withdrawing effect of the hydroxyl group, the electron
donating effect of one methyl group to the branched carbon atom in
22 G. Li, N. Li, Z. Wang, C. Li, A. Wang, X. Wang, Y. Cong and T. Zhang,
ChemSusChem, 2012, 5, 1958–1966.
HAA products of 2-MF with hydroxyacetone is weakened. As a result, 23 G. Li, N. Li, J. Yang, A. Wang, X. Wang, Y. Cong and T. Zhang,
Bioresour. Technol., 2013, 134, 66–72.
24 J.-P. Lange, E. van der Heide, J. van Buijtenen and R. Price, Chem-
the carbocation intermediate produced after the C–C cleavage
becomes less stable and the C–C cleavage reaction is restrained.
SusChem, 2012, 5, 150–166.
In this work, a brand new route for the synthesis of diesel or 25 R. Weingarten, G. A. Tompsett, W. C. Conner and G. W. Huber,
J. Catal., 2011, 279, 174–182.
26 K. A. Mauritz and R. B. Moore, Chem. Rev., 2004, 104, 4535–4586.
27 B. G. Harvey, M. E. Wright and R. L. Quintana, Energy Fuels, 2010,
jet fuel range branched alkanes was developed by the HAA of
2-MF with hydroxyacetone followed by the HDO. Among the
investigated solid acids, Nafion-212 resin exhibited the highest
24, 267–273.
c
This journal is The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 5727--5729 5729