Catalysis Communications 10 (2009) 17431746

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Production of alkanes from biomass derived carbohydrates on bi-functional

catalysts employing niobium-based supports
Ryan M. West, Mark H. Tucker, Drew J. Braden, James A. Dumesic *
University of Wisconsin-Madison, Department of Chemical and Biological Engineering, Madison, WI 53706, USA

a r t i c l e

i n f o

Article history:
Received 8 April 2009
Received in revised form 19 May 2009
Accepted 26 May 2009
Available online 2 June 2009
Keywords:
Niobic acid
Niobium phosphate
Bi-functional
Heterogeneous catalysis
Biomass
Sorbitol

a b s t r a c t
Bi-functional catalysts consisting of Pt supported on niobium-based solid acids were synthesized and utilized in the aqueous-phase dehydration and hydrogenation of sorbitol to alkanes at temperatures near
530 K and pressures of 54 bar. At low space velocities, the yield of alkanes is highest but decreases in
favor of oxygenated compounds as the space velocity is increased. Niobium-based catalysts demonstrate
superior reactivity in comparison to a silicaalumina based catalyst. This higher reactivity is not related
to the concentration of acid sites but rather is attributed to the coordination environment of the niobium
acid center.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Processing of renewable carbohydrates to produce fuels and/or
chemicals invariably requires the removal of oxygen to form compounds with lower molecular weights and higher volatility that
can be subsequently upgraded using gas-phase processes [1]. The
high water solubilities of carbohydrates, due to oxygenated functionalities, make aqueous-phase processing of these compounds
an attractive and necessary step. One strategy for the removal of
oxygenated groups is through dehydration of hydroxyl groups followed by hydrogenation of the resulting unsaturated species. This
process, denoted as aqueous-phase dehydration/hydrogenation
(APDH), can proceed over a bi-functional catalyst containing acidic
and metal components [2]. Dehydration over the acidic functionality creates unsaturated species such as C@C double bonds, C@O
double bonds, or in the case of 46 carbon species (e.g., 1,4-butanediol, and sorbitol) heterocyclic ring structures (e.g., tetrahydrofuran and isosorbide, respectively). These unsaturated species are
subsequently hydrogenated to fully saturated forms on the metal
component of the catalyst. Sequential cycling of these processes,
as shown schematically in Fig. 1 for the conversion of sorbitol to
hexane, leads to the eventual formation of saturated alkanes, the
Abbreviations: APDH, aqueous-phase dehydration/hydrogenation;
weight hourly space velocities.
* Corresponding author.
E-mail address: dumesic@engr.wisc.edu (J.A. Dumesic).
1566-7367/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2009.05.021

WHSV,

most thermodynamically stable product in the absence of CC

bond breaking [3,4].
Heterogeneously catalyzed aqueous-phase processing requires
robust acidic catalysts that are stable and active in hot liquid and
gaseous water environments. A previous study of APDH processing
of sorbitol at temperatures near 520 K and pressures near 50 bar
over a 4 wt% Pt silicaalumina catalyst demonstrated the principle
of converting sorbitol into alkanes [2]. This previous study using
Pt/silicaalumina was limited to low weight hourly space velocities (WHSV) of 0.0230.065 h 1 (where WHSV is dened as the
mass of reactant species per mass of catalyst per hour) to achieve
a high conversion to alkanes.
We recently carried out an investigation of potential solid acid
catalysts that would remain active for dehydration in both liquid
and gaseous water regimes using 2-butanol as a test molecule
[5]. Silicaalumina and the niobium-based catalysts, niobic acid
(Nb2O5nH2O) and niobium phosphate (NbOPO4), displayed high
activity for this model reaction. The high reactivity of niobium catalysts for reactions that either produce water or are conducted in
water have been noted in the literature [514]. It is generally
agreed that these catalysts are active and stable under these conditions [514], with niobium phosphate and phosphated niobic acid
showing higher reactivity than niobic acid [713].
The aim of the current study is to investigate the behavior of
niobium-based compounds in APDH of sorbitol solutions to produce alkanes in a ow system at 528 K and 54 bar, as compared
to the behavior of a silicaalumina catalyst. The performance of

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R.M. West et al. / Catalysis Communications 10 (2009) 17431746

C6H14O6

Hydrogenation / Reduction

-H2 O

C6H12O5

+H2

-H2 O

C6H10O4

+H2

C6H12O4

+H2

C6H14O4
-H2 O

-H2 O

C6H10O3

+H2

C6H12O3

+H2

C6H14O3

-H2 O

C6H10O2

-H2 O
+H2

C6H12O2

+H2

-H2 O

Hydrogen Production
C6H14O6 + 6H2O

Dehydration

-H2 O

C6H14O5

C6H10O1

13H2 + 6CO2

C6H14O2
-H2 O

+H2

C6H12O1

+H2

C6H14O1
-H2 O

C6H12

+H2

C6H14

Fig. 1. Catalytic processing of sorbitol on bi-functional catalysts to produce hexane via sequential dehydration and hydrogenation and to produce CO2 via reforming.

each catalyst is characterized by the yield to alkanes at increasing

ow rates of feed solution. Identifying catalysts that are effective in
forming saturated alkanes is of importance because APDH serves as
the nal step in the conversion of biomass-derived oxygenated
hydrocarbons to alkanes in the production of liquid transportation
fuel components [1,15,16].
2. Experimental
Catalysts of 2 and 4 wt% metal loading were prepared by incipient wetness of tetra-amine platinum nitrate (Aldrich) on amorphous silicaalumina (MCC 25, Grace Davidson with a Si/Al ratio
of 4), niobic acid (HY-340, Companhia Brasileira de Metalurgia e
Minerao (CBMM)) niobium phosphate (CBMM) or phosphated
niobic acid. As a typical example, the 4 wt% Pt silicaalumina catalyst was prepared by adding 0.4 g of Pt salt (0.2 g Pt) to 3.7 g of
water. This mixture was then added dropwise to 4.8 g of silicaalumina under constant mixing. The catalyst was dried overnight in
an oven and calcined in 20% oxygen in helium for 2 h at 533 K.
Phosphated niobic acid was prepared in a similar manner to previous reports [7,11,12,17]. In short, 120 mL of 0.84 M H3PO4 was stirred at room temperature with 6.35 g of niobic acid for 48 h. The
resulting paste was washed four times with 250 mL of water, dried
overnight at 393 K, and calcined in air at 723 K.
Experiments were carried out in an upow reactor and efuent
streams were quantied as described elsewhere [2,5,15,16].
Briey, catalysts were mixed with crushed silica to reduce dead
volume and packed between quartz wool in 1=4 inch stainless steel
reactors. The catalysts were rst reduced by ramping the temperature over 8 h to 723 K and holding for 2 h at 723 K under owing
H2, 250 cm3 (STP)/min. Reactivity studies were started by cooling
to 528 K under owing H2, increasing the pressure by simultaneously pressurizing above and below the catalyst bed, and then
introducing the aqueous sorbitol with an HPLC pump. All space
velocity studies were carried out in random order to ensure that
systematic deactivation was not occurring. Efuent compositions
were determined by combining the gas, aqueous and organic contributions. Typical carbon balances were closed to 100 10%.
Catalyst surface areas were determined from BET adsorption
isotherms of N2 at 77 K. The acid site density was determined by
temperature programmed desorption (TPD) of ammonia. Specically, 200 mg of catalyst was loaded into a glass ow reactor, pretreated at 573 K under owing helium, treated with 50 cm3 (STP)/
min of 1% ammonia in helium for 1.5 h at 423 K, and desorbed under helium at 423 K for 1 h (to remove physically bound ammonia).
The TPD spectrum was collected on-line using a mass spectrometer

with a helium carrier gas ow rate of 50 cm3 (STP)/min and a temperature ramp of 10 K/min from room temperature to 973 K, followed by holding at the nal temperature for 20 min.
3. Results and discussion
Fig. 1 shows possible APDH routes of sorbitol to hexane. Dehydration of oxygenated species (moving down in the gure) leads to
unsaturated species, while hydrogenation (moving right) restores
saturation. Many reaction paths are possible, as the production of
hexane requires six oxygen removal steps and six hydrogenation
steps. As more than 40 individual species were observed in this
study, the stoichiometric species shown in Fig. 1 are not specic
to one chemical. For instance, species observed with the stoichiometry of C6H12O1 include dimethyl-tetrahydrofuran, ethyl tetrahydrofuran, hexanones, and hexaldehyde. All of these species can
be hydrogenated to saturated alcohols which can then undergo
further dehydration and hydrogenation, eventually forming
hexane.
The ability to dehydrate oxygenated carbohydrates in aqueous
solutions is most easily represented by grouping the various intermediates in Fig. 1 by the number of oxygen atoms contained within each species (summing horizontal species). Fig. 2 illustrates the
change in carbon distribution between the grouped species from
Fig. 1 as a function of increasing feed rate. The top gure demonstrates the rates of production of the various species with increasing feed rate, while the bottom gure shows the carbon
distribution (normalized rate). The x-axes of the two gures are
proportional, with the sorbitol feed rate equal to the WHSV divided
by the molecular weight of sorbitol multiplied by 6 mol of C per
mol of sorbitol.
As seen in Fig. 2, the rate of alkane production is highest at low
space velocity and steadily decreases as the space velocity increases. The production of species with one or two oxygen atoms
slightly increases with increasing space velocity and then decreases in a similar manner as alkanes. Because multiple dehydrations are required to form these alkane species, the decrease in
production is expected as more highly oxygenated species formed
in this series of reactions compete for dehydration sites on the
acidic catalyst surface. The carbon distribution demonstrates these
same trends. The distribution to alkanes is highest at lower space
velocities and decreases as the ow rate is increased. The in situ
production of H2, a co-reagent in the APDH reaction, is accompanied by the production of CO2. The carbon distribution to CO2 decreased from approximately 15% at the lowest space velocity to
5% at the highest space velocity.

1745

120

C1H4 - C6H14

110

C1H4O - C6H14O

100

C5H8O2 - C6H14O2

90

C6H8O3 - C6H14O3

80

C6H10O4

70

C6H10O5 - C6H14O6

60

CO2

2wt% Pt Niobium Phosphate

4wt% Pt Niobium Phosphate
4wt% Pt Niobic Acid
4wt% Pt Phosphated Niobic Acid
4wt% Pt Silica Alumina

60%

50%

Yield to Alkanes

-1

-1

Rate of Production (C-mmol h gcat )

R.M. West et al. / Catalysis Communications 10 (2009) 17431746

50
40

40%

30%

20%

30
20

10%

10
0

0.2

10

20

30

40

50

60

70

80

90
-1

0.4

0.6

100 110 120

0.8

1.0

1.2

1.4

1.6

-1

WHSV (h )

-1

Sorbitol Feed Rate (C-mmol h gcat )

2wt% Pt Niobium Phosphate
4wt% Pt Niobium Phosphate
4wt% Pt Niobic Acid
4wt% Pt Phosphated Niobic Acid
4wt% Silica Alumina

40%

100%
90%

35%

Yield to Monofunctional

Carbon Distribution (%)

80%
70%
60%
50%
40%
30%

30%
25%
20%
15%
10%

20%
5%

10%

0%

0%
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

-1

WHSV (h )
Fig. 2. Inuence of increasing ow of a 25 wt% sorbitol feed over 0.73 grams of
4 wt% Pt on phosphated niobic acid catalyst at 528 K, 54 bar pressure with an
average molar ow of H2 to sorbitol of 13.5. Sorbitol feed rate is equal to the WHSV
divided by the molecular weight of sorbitol multiplied by 6 mol of C per mol of
sorbitol.

A comparison of a 4 wt% loading of Pt on the three niobiumbased catalysts and the silicaalumina-based catalyst is given in
Fig. 3, where the yield to alkanes and the yield to monofunctional
species are presented versus the feed rate of sorbitol into the system. In addition, the results for a 2 wt% Pt loading on niobium
phosphate are given to probe the effect of metal loading.
It is apparent from Fig. 3 that the niobium-based catalysts are
more effective at producing alkanes at all ow rates than the silicaalumina catalyst. Among the niobium catalysts, niobium phosphate and phosphated niobic acid are more active than niobic acid,
in accordance with previous literature reports [713]. The 2 wt% Pt
niobium phosphate catalyst demonstrated similar yields of alkanes
as the niobium catalysts with higher loadings of Pt, and these
yields are much higher than for the silicaalumina catalyst. The solid acid portion of the catalyst thus appears to have a stronger effect on the production of alkanes. This observation could be
economically advantageous as minimal loading of Pt is desired to
keep catalyst costs to a minimum. At reduced inlet ow, WHSV
of 0.40.6 h 1, the niobium catalysts were able to produce 50
60% total yield of alkanes from sorbitol (moles of C as alkanes di-

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

-1

WHSV (h )
Fig. 3. Yield of alkanes and monofunctional species with increasing feed rate of
sorbitol for 2.02.5 g of bi-functional catalysts at 528 K and 54 bar.

vided by moles of C in as sorbitol). In comparison, the SiAl catalyst

yielded only 20% alkanes at a WHSV of 0.2 h 1. The catalytic activity of the niobium catalysts remained high through the course of
testing over a period of 12 weeks, as determined by periodic repetition of studies at standard reaction conditions with similar
results.
Of additional interest is the production of monofunctional species from sorbitol [1,4]. In previous reports, approximately 50% of
the inlet sugar can be converted to hydrocarbons containing a single functional group such as alcohols, ketones, heterocycles or
acids. The hydrogen for this process is provided in situ with
approximately 3035% of the inlet carbon being reformed to CO2
and H2, such that approximately 70% of the non-reformed carbon
is reacted to monofunctional species. In the present paper, the
hydrogen is provided externally; however, approximately 10% of
the inlet carbon is reacted to CO2, see Fig. 2. From Fig. 3, it is apparent that the maximum yield to monofunctional compounds for the
niobium-based catalysts passes through a maximum of around 30%
as the space velocity is increased, such that approximately 35% of
the non-reformed carbon can create monofunctional species.
The low value for this maximum yield is due to the rapid reaction of the monofunctional species, likely through dehydration of
alcohols to form alkenes. As alcohols are consumed, the alcohol

1746

R.M. West et al. / Catalysis Communications 10 (2009) 17431746

Table 1
Physical properties of solid acid catalysts employed in this study; niobium catalysts from CBMM except where noted.
Recorded

Niobium
phosphate
Niobic acid
Phosphated niobic
acid
Silicaalumina
a

Literature

Acid site density

(umol/g)

BET surface area

(m2/g)

Acid site density

(umol/g)

BET surface area

(m2/g)

Initial heat of adsorption

ammonia (kJ/mol)

Initial heat of adsorption

pyridine (kJ/mol)

615

111

160 [8]

118180 [18,7]

75135 [10,8]

135
228

118
131

90131 [11,8]
270 [11]

108133 [8,18]
70170 [11,7]

50145 [10]

100a [19]

578

498

181 [20]

220 [20]

Precipitated from niobium ethoxide solution [19].

ketone equilibrium is shifted and the ketones present in the system

are hydrogenated to alcohols, followed by further dehydration,
thereby limiting the yield to monofunctional species. The absence
of a strong acid group in previous reports [1,4] allowed the accumulation of monofunctional species. Thus the presence of strong
acidic groups, such as niobium phosphate and niobic acid, is effective for the production of alkanes due to the high rate of dehydration, but under the conditions of this report, these catalytic sites
are not effective for high yields to monofunctional species for this
same reason. Silicaalumina, on the other hand, shows a rapid increase in the production of monofunctional compounds at decreasing space velocity. While this trend appears to be different from
the niobium catalysts, it is known that further decreases in the
space velocity (0.0230.065 h 1) allow for near complete conversion to alkanes [2], and the monofunctional yield decreases
accordingly.
The measured and literature values for the initial surface properties of the acidic catalyst supports are given in Table 1. All of the
niobium-based catalysts have relatively low surface areas. In a previous study, it was found that the surface area of silicaalumina
and a comparable niobium phosphate decreased to 169 and
85 m2/g, respectively, after exposure to liquid water at high temperature and pressure [5] similar to the conditions of this study.
The catalysts remained active in both the previous case and the
study conducted here despite this decrease, suggesting that the
low surface area catalysts remain quite active. One possible area
of improvement the system might therefore be found by synthesis
of niobium-based compounds with higher surface area that remains stable under aqueous conditions.
The catalysts employed in this study span a wide range of acid
site densities. However, the niobium-based catalysts are more active in producing alkanes, despite having similar or fewer acid sites
per gram than silicaalumina. Comparing the initial heats of
adsorption of basic probe molecules on these catalysts does not
clarify why niobium is more effective. As shown in Table 1, both
ammonia and pyridine bind more strongly to silicaalumina than
to niobium catalysts [8,10,19,20]. The relationship between the
heat of adsorption and reactivity is not always direct [20,21], and
the high activity of niobium, despite its lower heat of adsorption
and lower acid concentration, provides one such example.
In a recent comparative study, niobium catalysts were able to
retain strong acid functionality in both apolar and highly polar
media [8]. This behavior suggests a strong interaction of niobium
with reactive molecules (e.g. alcohols) and a lower interaction with
the solvent (e.g., water), a trend observed in the desorption of
water and methanol from niobium surfaces, where methanol desorbs at a higher temperature [22]. The acidic sites of niobiumbased compounds involve a Nb@O group, or a hydroxyl group asso-

ciated with a Nb@O group [23,24]. Thus, the high activity of niobium-based compounds could be due to the interaction of
reactive molecules with Nb@O and adjacent hydroxyl groups in a
similar manner as the pushpull mechanism predicted for vanadium oxides [25]. These unique properties of the surface acidic
groups on niobium lead to higher rates for dehydration of oxygenated carbohydrates in aqueous media compared to the rates for silicaalumina. At low space velocities, 0.20.6 h 1, niobium-based
catalysts can achieve over 50% yield of sorbitol to alkanes, while
only 520% yield is observed with silicaalumina.
Acknowledgements
Supported by US Department of Energy Ofce of Basic Energy
Sciences and the National Science Foundation Chemical and Transport Systems Division of the Directorate for Engineering. We also
thank E.L. Kunkes and J.Q. Bond for technical assistance.
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