Synthesis of Diesel and Jet Fuel Range Alkanes with Furfural and Angelica Lactone

Article abstract of DOI:10.1021/acscatal.7b01992

A route was developed for the synthesis of diesel and jet fuel range C₉ and C₁₀ alkanes with furfural and angelica lactone, which can be obtained from hemicellulose and cellulose. It was found that angelica lactone is more reactive than levulinic acid or its other derivates in the aldol condensation with furfural. Among the investigated catalysts, Mn₂O₃ was found to be the most active and was very stable for the aldol condensation of furfural and angelica lactone. Over Mn₂O₃, a high carbon yield of C₁₀ oxygenates (about 96%) can be achieved by the aldol condensation of furfural and angelica lactone under mild conditions (353 K, 4 h). By the hydrogenation and hydrodeoxygenation of the aldol condensation product over the Pd/C and Pd-FeO_x/SiO₂ catalysts, high carbon yields (～96%) of C₉ and C₁₀ alkanes were obtained.

Full text of DOI:10.1021/acscatal.7b01992

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Article
Synthesis of Diesel and Jet Fuel Range
Alkanes with Furfural and Angelica Lactone
Jilei Xu, Ning Li, Xiaofeng Yang, Guangyi Li, Aiqin Wang, Yu Cong, Xiaodong Wang, and Tao Zhang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b01992 • Publication Date (Web): 26 Jul 2017
Downloaded from http://pubs.acs.org on July 28, 2017
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Synthesis of Diesel and Jet Fuel Range Alkanes with
Furfural and Angelica Lactone
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Jilei Xu,† Ning Li,†,‡,* Xiaofeng Yang,† Guangyi Li,† Aiqin Wang,†,‡ Yu Cong,† Xiaodong Wang,† and Tao
Zhang†,‡,*
†State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian 116023, China.
‡iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
ABSTRACT: A route was developed for the synthesis of diesel and jet fuel range C9 and C10 alkanes
with furfural and angelica lactone which can be obtained from hemicellulose and cellulose. It was found
that angelica lactone is more reactive than levulinic acid or its other derivates in the aldol condensation
with furfural. Among the investigated catalysts, Mn2O3 was found to be the most active and very stable
for the aldol condensation of furfural and angelica lactone. Over it, high carbon yield of C10 oxygenates
(about 96%) can be achieved by the aldol condensation of furfural and angelica lactone under mild
conditions (353 K, 4 h). By the hydrogenation and hydrodeoxygenation of the aldol condensation product
over the Pd/C and Pd-FeOx/SiO2 catalysts, high carbon yields (~96%) of C9 and C10 alkanes were
obtained.
KEYWORDS: lignocellulose, diesel and jet fuel, angelica lactone, aldol condensation,
hydrodeoxygenation
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Introduction
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With the increasing of social concern about the energy and environmental problems, the catalytic
conversion of renewable and inedible biomass to fuels1 and chemicals2 has become a hot research topic.
Lignocellulose is the main component of agricultural and forestry wastes. Compared with other forms of
biomass, lignocellulose is much cheaper and more abundant. Diesel and jet fuel are two kinds of often
used transportation fuels. Following the pioneering work of Dumesic,3 Huber4 and Corma,5 the synthesis
of diesel and jet fuel range hydrocarbons with the lignocellulose derived platform compounds has drawn
tremendous attention.6
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Furfural and levulinic acid are two important platform compounds which have been produced in
industrial scale by the hydrolysis/dehydration of the hemicellulose and cellulose.7 Angelica lactone is the
dehydration product of levulinic acid.6g, 6j In this work, a C10 oxygenates (i.e. compound 1A in Scheme 1)
was obtained by the solvent-free aldol condensation of furfural and angelica lactone. Compared with
levulinc acid, methyl levulinate and γ-valerolactone, angelica lactone is more reactive in the aldol
condensation with furfural. Among the invesigated catalysts, Mn2O3, an amphoteric metal oxide which
has low acidity and low basity, was found to be the most active and stable for the aldol condensation
reaction. The C10 oxygenate as obtained was further hydrogenated and hydrodeoxygenated to C9 and C10
alkanes. The stragey of this work is proposed in Scheme 1.
Scheme 1. Stragey for the Synthesis of C9 and C10 Alkanes with Furfural and Angelica Lactone
which can be Derived from Hemicellulose and Cellulose.
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Results and Discussion
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In the first part of this work, we investigated the solvent-free aldol condensation of furfural and
angelica lactone over a series of metal oxides. To facilitate the comparsion, we fixed the ratio of metal
atom in the catalyst to molecule of furfural (or angelica lactone) in the feedstock as 1: 5. According to the
analysis of HPLC and NMR spectra (see Figure S1 and Figure S2 in supporting information), 3-(furan-2-
ylmethylene)-5-methylfuran-2(3H)-one (i.e. compound 1A in Scheme 1) was identified as the main
product from the solvent-free aldol condensation of furfural and angelica lactone. This compound has the
carbon chain length of diesel and jet fuel range. Therefore, it can be used as a potential precursor in the
synthesis of renewable diesel and jet fuel. Among the investigated metal oxide catalysts, Mn2O3
exhibited the highest acitivity and selectivity for the aldol condensation of furfural and angelica lactone
(see Figure 1). Over this catalyst, furfural was completely converted and high carbon yield of 1A (96%)
was acheived after the reaction was carried out at 353 K for 4 h.
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Cr 2
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Figure 1. Conversions of furfural, carbon yields and selectivities of 1A over different metal oxide
catalysts. Reaction conditions: 10 mmol angelica lactone, 10 mmol furfural, 2 mmol MgO, ZnO, TiO2,
SnO2 or 1 mmol Mn2O3, La2O3, Fe2O3, Cr2O3, Nb2O5; 353 K, 4 h.
Besides the Mn2O3 catalyst, the La2O3, MgO and ZnO catalysts were also found to be highly active for
the aldol condensation of furfural and angelica lactone. Over them, furfural was compeletely converted.
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However, the selectivities of 1A over these catalysts were slightly lower than that over the Mn2O3 catalyst,
which leads to the lower carbon yields of 1A over these catalysts. Compared with the La2O3, MgO and
ZnO catalysts, the Fe2O3 catalyst is more selective for the aldol condensation of furfural and angelica
lactone, but this catalyst is still less active and selective than the Mn2O3 catalyst.
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Subsequently, we also compared the catalytic performances of different manganese oxides for the aldol
condensation of furfural and angelica lactone. To do this, we chose MnO, Mn2O3 and MnO2 as
representatives for manganese oxides with different valence states. From the results illustrated in Figure 2,
we can see that all of these manganese oxides are active for the aldol condensation of furfural and
angelica lactone. Under the investigated reaction conditions, furfural was compeletly converted, high
carbon yields (> 65%) of 1A were acheived over these catalysts. The carbon yields (or selectivity) of 1A
over these manganese oxides decreases in the order of decrease in the order of Mn2O3 > MnO2 > MnO.
From the XRD patterns of the used catalysts (see Figure S3 in supporting information), it was noticed that
the Mn2O3 and MnO kept same but a part of MnO2 was reduced to Mn2O3 (which was labeled by black
diamond in Figure S3c) after being used in the activity tests. Based on these results, we think that the
Mn2O3 is the most active sites for the aldol condensation of furfural and angelica lactone.
Furfural conversion (%)
Carbon yield of 1A (%)
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Mn2O3
MnO
MnO2
Figure 2. Conversions of furfural, carbon yields of 1A over different manganese oxide catalysts. Reaction
conditions: 10 mmol angelica lactone, 10 mmol furfural, 2 mmol MnO, MnO2 or 1 mmol Mn2O3; 353 K,
4 h.
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As we know, levulinic acid is the feedstock in the production of angelica lactone. Methyl levulinate and
γ-valerolactone can be obtained by the esterification or hydrogenation of levulinic acid.8 In this work, we
also studied the solvent-free aldol condenstaion of these compounds with furfural. The reactions were
carried out over the Mn2O3 catalyst under the same reaction conditions (353 K, 4 h) as what we used for
the aldol condensation of furfural and angelica lactone. From the analysis of HPLC, no aldol
condensation product was identified, which means that these compounds do not react with furfural under
the investigated conditions. Based on these results, we can see that the reactivity of angelica lactone is
evidently higher than levulinic acid, methyl levulinate and γ-valerolactone, which is advantagous in the
industrialized production of diesel and jet fuel precursor. The relatively higher reactivity of angelica
lactone can be rationalized by the higher stability of carbanion which is caused by its conjugate chemical
structure. According to the DFT calculation results illustrated in Figure 3 and the Table S1 of supporting
information, the energy difference between angelica lactone and its carbanion is evidently lower than
those between the levulinic acid, methyl levulinate, γ-valerolactone and corresponding carbanions, which
may be the reason for the higher reactivity of angelica lactone.
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Figure 3. Energy differences between γ-valerolactone, angelica lactone, methyl levulinate and their
corresponding carbanions. The detail information for the DFT calculation was given in supporting
information. The white balls, grey balls and red balls in the figure account for hydrogen atoms, carbon
atoms and oxygen atoms, respectively.
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In the previous work of Wang et al.9 and our group10, C15 and C10 diesel and jet fuel precursors have
been synthesized by the aldol condensation of isopropyl levulinate (or sodium levulinate) and furfural.
Compared with these routes, the new route reported in this work has disadvantange because it contaions
an additional levulinic acid dehydration step for the production of angelica lactone. However, the new
route doesn’t need to neutralization the aldol condensation product with acid before HDO process. This
will reduced the cost of acid and the waste of sodium salt which will generated as a by-product.
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Figure 4. Conversion of furfural and carbon yield of 1A over the Mn2O3 catalyst as a function of recycle
time. Reaction conditions: 10 mmol angelica lactone, 10 mmol furfural, 1 mmol Mn2O3; 353 K, 2 h.
The stability of Mn2O3 catalyst in the solvent-free aldol condensation of furfural and angelica lactone
was investigated. To do this, the Mn2O3 catalyst was repeatedly used in the solvent-free aldol
condensation of furfural and angelica lactone under the reaction conditions when ~55% furfural
conversion was acheived over the fresh Mn2O3 catalyst. After each usage, the catalyst was throughly
washed with ethanol and dried at 333 K for 8 h. According to Figure 4, the Mn2O3 catalyst was stable
under the investigated conditions. No evident deactivation was observed during 5 usages. According to
ICP result, small amount of Mn was identified in the aldol condensation product. Based on these results,
we believe that there is leaching of Mn during the reaction. However, the leaching of Mn species during
the reaction has no evident influence the activity of the Mn2O3 catalyst. In the most of previous work
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about the aldol condensation of furfural over heterogenous catalysts,11 the activity of catalyst decreased
due to the Cannizzaro reaction (or polymerization) of furfural. To overcome this problem, the catalysts
must be regnerated at higher temperature in oxidative atomophere to remove the organic compounds
which were strongly adsorbed on the catalysts. Compared with those reaction systems, the regenaration of
catalyst in this reaction system is much easier. This is advantageous in future application.
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To figure out the reason for the excellent performance of the Mn2O3 catalyst, we characterized it by
CO2-TPD and NH3-TPD. From the results shown in the Figure S4 of the supporting information, we can
see that the Mn2O3 is an amphoteric metal oxide which has weak acid sites and weak base sites at the
same time. This may be the reason for the higher activity and selectivity of the Mn2O3 catalyst in the aldol
condensation of furfural and angelica lactone. As we know, furfural will polymerize in the presence of
strong acid sites, which will lead to the lower activity and selectivty to 1A over strong acid catalysts (such
as Nb2O5 and Cr2O3). Analogously, the metathetical reaction between angelica lactone and strong base
sites (or the Cannizzaro reaction of furfural catalyzed by strong base sites) will also decrease the activity
and selectivty to 1A over strong base catalysts (such as MgO and La2O3). In this work, the Mn2O3 catalyst
has proper acid strength and base strength which are effective for the aldol condensation of furfural and
angelica lactone but not enough for the polymerization of furfural and the metathetical reaction of
angelica lactone (or the Cannizzaro reaction of furfural). This may be one reason for the excellent
performance of Mn2O3 in the aldol condensation of furfural and angelica lactone. Furthermore, as what
has been suggested in literature,6m, 12 the synergism effect between acid sites and base site is benefical for
the aldol condensation reactions. Therefore, the simultaneous presence of acid site and base site on the
surface of Mn2O3 may be another reason for the high activity of Mn2O3 in the aldol condensation of
furfural and angelica lactone.
The reaction mechanism for the aldol condensation of furfural and angelica lactone was proposed in
Scheme 2. In the first step, the angelica lactone is adsrobed and deprotonated to carbanion on the base
sites of Mn2O3. In the second step, the carbanion attacks the carbonyl group of furfural which is adsorbed
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on the acid sites of Mn2O3. As Corma et al. suggested previously,13 weak acid site has activation effect on
the carbonyl group (by polarizing the C=O bond and increasing the eletrophilicity of the carbonyl group),
which will decrease the energy barrier for the condensation of this molecule with a carbanion. In the third
step, the product generated in the second step was protonated and dehydrated to 1A.
Scheme 2. Reaction Mechanism for the Aldol Condensation of Furfural and Angelica Lactone over
the Mn2O3 Catalyst.
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Subsequently, we also explored the solvent-free aldol condensation of angelica lactone and other
lignocellulose derived carbonyl compounds. Among them, the 5-hydroxylmethylfurfural can be obtained
from the hydrolysis/dehydration of cellulose14. Benzene formaldehyde is a representative of the aldehydes
which can be obtained from lignin.15 Acetone can be produced from the ABE fermentation of
lignocellulose.16 Butanal can be produced from the partial oxidation of dehydrogenation of the bio-
butanol. Cyclopentanone can be obtained from the aqueous phase selective hydrogenation of furfural.17
From the results listed in Table 1, we can see that angelica lactone can react with the investigated
aldehydes under mild conditions (353 K, 4 h). From these reactions, several C9-C12 oxygenates can be
obtained. As a potential application, these compounds can be used as the precursors for the synthesis of
renewable diesel and jet fuel. Compared with aldehydes, ketones have lower reactivity. Under the same
reaction conditions, no aldol condensation products were obtained over the Mn2O3 catalyst when acetone
and cyclopentanone were used as the feedstocks. This phenomena can be explained by two reasons: 1) As
we know, the carbonyl groups of aldehydes are connected with a alkyl group and a hydrogen atom, while
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the carbonyl groups of ketones are connected with a alkyl groups. Because the alkyl groups have higher
electronic effect than hydrogen atom, the carbonyl groups in aldehydes are more electrophilic and easier
to be attacked by the carbanion generated from the deprotonation of angelica lactone than those in
ketones. 2) The alkyl groups are larger than hydrogen atom. From the pointview of steric effect, the
carbonyl groups in aldehydes are also easier to be attacked by the carbanion than those in ketones. Due to
these reasons, 5-hydroxylmethylfurfural, butanal, and benzene formaldehyde are more reactive in the
aldol condensation with angelica lactone. Analogously, we also investigated the solvent-free aldol
condensation of furfurl and its partial oxidization prouct 2(5H)-furanone18 (which has similar chemical
structure as angelica lactone). It was found that this compound is less reactive than angelica lactone.
Under the investigated conditions, the furfural conversion (1.8%) over the Mn2O3 catalyst is very low. No
C9 oxygenate from the aldol condenation of furfural and 2(5H)-furanone was obtained.
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Table 1. Conversions of carbonyl compounds and the carbon yields of aldol condensation products from
the reactions of angelica lactone with various lignocellulosic carbonyl compounds. Reaction conditions:
10 mmol angelica lactone, 10 mmol carbonyl compound, 1 mmol Mn2O3; 353 K, 4 h.
Reactant
Product
Conversion (%)
100
Carbon yield (%)
75.7
100
100
77.9
68.9
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As the final aim of this work, we investigated the catalytic conversion of 1A to diesel and jet fuel range
alkanes. Because 1A is a solid at room temperature (see Figure S5a in supporting information), it can’t be
delivered by HPLC pump. To increase the fluidity of 1A, we hydrogenated it before the solvent-free
hydrodeoxygenation (HDO) tests (the detail information of the hydrogenation step was given in support
information). From the analysis of the hydrogenation products with GC-MS (see Figure S6 and Figure S7
in supporting information), it was found that 1A was totally converted to a mixture of 3-(5-
hydroxypentyl)-5-methyldihydrofuran-2(3H)-one and 3-(2-hydroxypentyl)-5-methyldihydrofuran-2(3H)-
one (i.e. 1B and 1C in Scheme 3) after being hydrogenated over the Pd/C catalyst at 433 K. The
hydrogenation products exist as liquid at room temperature and can be directly used for the solvent-free
HDO (see Figure S5b).
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Scheme 3. Reaction Pathway for the Generation of 1B and 1C from the Hydrogenation of 1A.
The solvent-free HDO tests of hydrogenated 1A (i.e. a mixture of 1B and 1C) were carried out over the
Pd/SiO2, Pd-FeOx/SiO2 and FeOx/SiO2 catalysts at 623 K. From the analysis of the HDO products, it was
noticed that the 1B and 1C were completely converted over these catalysts. High carbon yields of diesel
and jet fuel range C8-C10 alkanes were achieved over the Pd/SiO2 and Pd-FeOx/SiO2 catalysts. These
alkanes have jet fuel range carbon chain length and low freezing points (see Table S2). Therefore, they
can be directly blended into conventional jet fuel without hydroisomerization. In contrast, the 1B and 1C
were only partially hydrodeoxygenated over the FeOx/SiO2 catalyst (see Figure S8 in supporting
information).
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C5-C7 gasoline range
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fuel range alkanes
Pd-FeOx/SiO2
FeOx/SiO2
Pd/SiO2
Figure 5. Carbon yields of different alkanes from the solvent-free HDO of hydrogenated 1A over the
Pd/SiO2, Pd-FeOx/SiO2 and FeOx/SiO2 catalysts. Reaction conditions: 623 K, 6 MPa, 1.8 g catalyst; liquid
feedstock flow rate 0.033 mL min-1, hydrogen flow rate: 120 mL min-1.
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Figure 6. Carbon distributions of the alkane products from the HDO of hydrogenated 1A over the
Pd/SiO2 (a) and Pd-FeOx/SiO2 (b) catalysts. Reaction conditions: 623 K, 6 MPa, 1.8 g catalyst; liquid
feedstock flow rate 0.033 mL min-1, hydrogen flow rate: 120 mL min-1.
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It is interesting that the carbon yield of C8-C10 alkanes over the Pd-FeOx/SiO2 catalyst is higher than
that over the Pd/SiO2 catalyst (see Figure 5). From Figure 6, it is noticed that there is also big difference
between the carbon distributions of the alkane products over the Pd/SiO2 and Pd-FeOx/SiO2 catalysts.
Over the Pd/SiO2 catalyst, the HDO products were mainly composed of C8 and C9 alkanes. In contrast,
C10 alkanes was obtained as the predominate HDO product over the Pd-FeOx/SiO2 catalyst. According to
our previous work on the HDO of other furan compounds,19 these results can be explained becuase the
presence of Fe species not only promoted the HDO reaction, but also restrained the decarbonylation and
the decarboxylation which will lead to the generation of C8 and C9 alkanes (see Scheme 4).
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Scheme 4. Reaction Pathways for the Generation of C8 and C9 Alkanes during the HDO of 1B and
1C.
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Undecane
Dodecane
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Pd-FeOx/SiO2
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Figure 7. Carbon yields of alkanes from the HDO of ethyl laurate over the Pd/SiO2 and Pd-FeOx/SiO2
catalysts. Reaction conditions: 623 K, 6 MPa, 1.8 g catalyst; liquid feedstock flow rate 0.033 mL min-1,
hydrogen flow rate: 120 mL min-1.
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In the previous work of Resasco et al. and our group,19-20 the restraining effect of Fe species on the
decarbonylation over Ni and Pd catalysts has been proved. In this work, the inhibition effect of iron
species on the decarboxylation over the Pd catalyst was further verified by the solvent-free HDO of ethyl
laurate. According to the Figure 7 and Figure S9 in supporting information, the main HDO product over
the Pd/SiO2 catalyst was undecane, while the major HDO product over the Pd-FeOx/SiO2 catalyst was
dodecane. This result indicated that the modificiation of Pd/SiO2 catalyst with Fe species can evidently
restrain the decarboxylation during the HDO process.
Conclusion
In summary, the solvent-free aldol condensation of furfural and angelica lactone followed by
hydrogenation and hydrodeoxygenation (HDO) is a promising way for the production of renewable diesel
and jet fuel range alkanes. Compared with levulinic acid and its other derivates, angelica lactone is much
more reactive, which is advantageous in real application. Mn2O3 was found to be a highly active and
stable catalyst for the solvent-free aldol condensation of furfural and angelica lactone, which can be
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explained by its proper acid and base strengths. Over the Mn2O3 catalyst, a series of diesel and jet fuel
precursors can be obtained by the solvent-free aldol condensation of angelica lactone and lignocellulosic
aldehydes. The aldol condensation product of furfural and angelica lactone was further hydrogenated and
hydrodeoxygenated to diesel and jet fuel range alkanes over Pd catalysts. The modification of Pd/SiO2
catalyst with iron species increases its HDO activity and restrains the unexpected decarbonylation and
decarboxylation during the HDO process. Both effects lead to the high carbon yield of diesel and jet fuel
range alkanes over the Pd-FeOx/SiO2 catalyst.
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ASSOCIATED CONTENT
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Supporting Information.
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The following files are available free of charge.
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Experimental details. Characterization of the catalysts. Copies of HPLC, GC chromatograms and
NMR spectra. (PDF)
AUTHOR INFORMATION
Corresponding Author
*T.Z.: taozhang@dicp.ac.cn;
*N.L.: lining@dicp.ac.cn.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foundation of China (no. 21603221;
21690082; 21690084; 21506213; 21476229; 21277140), Dalian Science Foundation for
Distinguished Young Scholars (no. 2015R005), the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB17020100), Department of Science and Technology of
Liaoning Province (under contract of 2015020086-101). Dr. Xu appreciates the Postdoctoral
Science Foundation of China (2015M580235) and the dedicated grant for methanol conversion
from DICP for funding this work.
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