View Article Online / Journal Homepage / Table of Contents for this issue

PAPER www.rsc.org/greenchem | Green Chemistry

Enhancing the selectivity of the hydrogenation of naphthalene to tetralin by

high temperature water
Yan Cheng,a Honglei Fan,a Suxiang Wu,a Qian Wang,a Jin Guo,a,b Liang Gao,c Baoning Zongc and
Buxing Han*a
Received 13th March 2009, Accepted 23rd April 2009
First published as an Advance Article on the web 7th May 2009
Published on 07 May 2009. Downloaded by Michigan State University on 06/08/2013 19:29:21.

DOI: 10.1039/b904305e

Enhancing selectivity and an efcient use of feedstocks in chemical reactions using greener
methods is an important aspect of green chemistry. In this work, we conducted the hydrogenation
of naphthalene to produce tetralin catalyzed by a cheap FeMo based catalyst with and without
high temperature water (HTW). The effects of various factors on the reaction, such as density of
water, reaction temperature, reaction time and amounts of catalyst, were investigated. It was
demonstrated that the addition of water could increase the yield of tetralin and suppress
formation of coke effectively. The reaction in the presence of D2 O indicated that H/D exchange
occurred during the reaction process.

Introduction elds.2830 Tetralin can be synthesized in a complicated Bergman

Investigations of high temperature water (HTW) as an environ-
mentally benign medium for chemical reactions are attracting
more and more attention in recent years. This is not only because
it is cheap, naturally abundant and nontoxic but also because
its physicochemical properties can be tuned with pressure and
temperature. This means that the properties of the medium
can be tuned without changing its composition.14 HTW has
been used in destruction of organic wastes,5,6 preparation of
synthetic natural gas from biomass,7 crystalline-to-amorphous
transformation of cellulose,8 recovery of phenolic compounds
through the decomposition of lignin,9 hydrothermal synthesis
of metal oxide nanoparticles,1013 etc. HTW-based organic
chemistry is attractive because it is consistent with several goals
of green chemistry and green engineering.2,14,15 Up to now, some
organic chemical reactions have been carried out in HTW, such
as Beckmann rearrangements,16 crossed aldol condensations,17
ene reactions,18 bisphenol A cleavage,19 synthesis of terephthalic
acid,20 oxidation of methylaromatics,21 oxidation of benzoic acid
to phenol,22 hydrogenation of different compounds,23,24 synthesis
of e-caprolactam from 6-aminocapronitrile,25 catalytic selective
partial oxidation using O2 for the synthesis of carboxylic acids,26
and chemical reactions of C-1 compounds.27
1,2,3,4-Tetrahydronaphthalene (tetralin) is a very useful high
boiling point solvent which has been widely used in paint, coat-
ings, inks, pharmaceuticals, paper, hydrogen donors and in other
a studied and used as a source of H2 for different hydrogenation
Beijing National Laboratory for Molecular Sciences, Institute of
Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
E-mail: hanbx@iccas.ac.cn; Fax: +86 10-62559373; Tel: +86
10-62562821
b
China University of Mining & Technology, Beijing, 100190, China
c
Research Institute of Petroleum Processing, Sinopec, Beijing, 100083,
China
Electronic supplementary information (ESI) available: NMR data for
the reaction product. See DOI: 10.1039/b904305e
cyclization or simply through the hydrogenation of naphthalene
in the presence of noble metals or transition metals.3135 The
reaction catalyzed by noble metals (e.g. platinum) usually shows
high selectivity to tetralin because naphthalene interacts with
surface metals strongly and prevents the hydrogenation of
tetralin.36 However, it is known that noble metals are much
more expensive than transition metals. Transition metals are
cheaper, but the selectivity to tetralin is low. How to enhance the
selectivity of the reaction catalyzed by cheaper transition metal
based catalysts is an interesting topic.
In the present work, the hydrogenation of naphthalene to
produce tetralin using a FeMo based catalyst was studied
with and without HTW. It was demonstrated that water could
enhance the selectivity of tetralin and suppress the formation of
coke signicantly under suitable conditions, i.e., when water was
used as a green solvent or additive, the feedstock can be used
much more effectively and the selectivity of the desired product
is much higher.
Results and discussion
The main focus of this study is the impact of water on the
hydrogenation of naphthalene to produce tetralin. The inuence
of different factors such as the density of the water, the reaction
temperature, the reaction time and the loading of catalyst was
studied. The thermal decomposition of formic acid has been
reactions.24,37,38 It was shown that on the laboratory scale, this
approach is a simple, convenient, and safe method to carry out
hydrogenation reactions. In this work, formic acid was also used
as the source of H2 . The conversion of naphthalene is dened as
the weight percent of converted naphthalene, and the yield of a
product is the weight percent of naphthalene converted into the
corresponding product.

This journal is The Royal Society of Chemistry 2009 Green Chem., 2009, 11, 10611065 | 1061

XRD pattern of the catalyst
The catalyst was prepared following the procedures reported
in the literature.39 The XRD pattern of the prepared catalyst
determined is presented in Fig. 1, together with the standard
stick pattern of Fe2 (MoO4 )3 . Obviously, the pattern agreed
well with the standard pattern, indicating that the catalyst was
Fe2 (MoO4 )3 .
Published on 07 May 2009. Downloaded by Michigan State University on 06/08/2013 19:29:21.
Fig. 1 XRD pattern of the prepared catalyst (top) and the standard
stick pattern of Fe2 (MoO4 )3 (bottom).
Effect of water density
The inuence of the water density on the reaction was studied at
606 K. The results with 12.8 mg and 100.0 mg of naphthalene in
the reactor are given in Fig. 2 and 3, respectively. The density of
the water was varied from 0 (without water) to 0.20 g mL-1 .
The density of the water was calculated from the mass of
water charged divided by the volume of the reactor (6.1 mL).
The gures show that in the absence of water the yield of the
product tetralin was low. With an increase of the water density
in the system, the yield of the product increased considerably.
Our experiments showed that decalins, which were the fully
hydrogenated product, were also produced. Other byproducts
were mainly coke with a very small amount of other compounds,
and we classied them as coke in the gures and in the following
discussion for simplicity. Therefore, the amount of coke was
easily calculated from the mass of the naphthalene charged, and
the amounts of the naphthalene, tetralin and decalins after the
reaction were determined by GC analysis. Fig. 2 and 3 show that
Fig. 2 Effect of water density on naphthalene conversion and the yields
of different compounds (12.8 mg naphthalene, 6.6 mg catalyst, 0.28 mL
formic acid, 5 h, 606 K).
1062 | Green Chem., 2009, 11, 10611065
View Article Online
Fig. 3 Effect of water density on naphthalene conversion and the
yields of different compounds (100.0 mg naphthalene, 10.0 mg catalyst,
0.50 mL formic acid, 4 h, 606 K).
the amounts of decalins and coke decrease with an increase of
the water density.
We can also see that with increasing water density, the
conversion of naphthalene decreased slightly at the beginning
and decreased quickly as the water density exceeded about
0.082 g mL-1 . It can be known from the saturate vapour pressure
of water and the density of steam,40 that liquid water appeared as
the density of water exceeded 0.082 g mL-1 at this temperature.
In other words, the water existed only in the vapour phase as
the density of water was less than about 0.082 g mL-1 , and
some water began to liquefy as the density was larger than
0.082 g mL-1 . Therefore, the main reason for the abrupt decrease
in the conversion may be that liquid water covered the surface
of the catalyst, which reduced the mass transfer of the reactants.
It should be mentioned that water may affect the decomposition
of formic acid and the amount of hydrogen produced under
our experimental conditions.24 Therefore, in order to keep a
large amount of hydrogen in the reactor during the reaction,
the amount of formic acid charged was in large excess in our
experiments.
Fig. 2 and 3 show that the effect of water on the conversion and
yield is less pronounced at a higher naphthalene concentration.
The main reason for the difference may be that the amounts
of naphthalene, catalyst, and formic acid at the different
naphthalene concentrations were different. However, Fig. 2 and
3 show clearly that water can reduce the formation of coke
effectively at different reactant concentrations, and the density
of water affects the selectivity more signicantly at the point
around the phase separation.
In order to study the effect of water on the yield of the
products at the same conversion of naphthalene, we determined
the conversion and the yields at different reaction times in the
absence of water, and the results are presented in Fig. 4. It can
be seen by comparing Fig. 2 and 4 that the yield of tetralin
in the presence of water was considerably higher than that
without water at a similar conversion of naphthalene, and the
amount of coke produced in the absence of water was much
larger. The maximum yield of tetralin could reach 85% with
water, while in the absence of water was only about 60%. The
main reason was that the addition of water could effectively
suppress the formation of coke. Therefore, the reactant can be
used more effectively in the presence of water. The mechanism
for producing coke is very complex even in the absence of water.41
This journal is The Royal Society of Chemistry 2009

Published on 07 May 2009. Downloaded by Michigan State University on 06/08/2013 19:29:21.
Fig. 4 Effect of reaction time on naphthalene conversion and the yields
of different compounds in the absence of water (12.8 mg naphthalene,
0.28 mL formic acid, 6.6 mg catalyst, 606 K).
The reasons for reducing the amount of coke after adding water
need to be studied further.
Effect of the reaction temperature
The effect of the reaction temperature was also evaluated at a
water density of 0.082 g mL-1 , and the results are shown in Fig. 5.
When the reaction temperature increased from 547 to 606 K,
the conversion of naphthalene increased to a maximum and
then decreased slightly with a further increase in temperature.
The temperature affects the conversion in different ways. First,
the reaction should be faster at higher temperatures due to
the reduction of the activation energy. Second, the amount of
liquid water decreased with an increase of temperature as the
temperature was lower than 606 K, because liquid water existed
in the reactor when the temperature was below 606 K. Both of
the factors are favourable to enhance the reaction rate. Third, at
606 K, liquid water disappeared as discussed above and there was
no liquid water at higher temperature. But a higher temperature
is unfavourable for the thermodynamic equilibrium of naph-
thalene hydrogenation, since the hydrogenation is exothermic.42
The competition of the above factors resulted in the maximum
conversion at 606 K.
Fig. 5 Effect of reaction temperature on naphthalene conversion
and the yields of different compounds (0.082 g mL-1 water, 12.8 mg
naphthalene, 0.28 mL formic acid, 6.6 mg catalyst, 5 h).
Effect of the reaction time
Fig. 6 shows the effect of reaction time on the conversion of
naphthalene and the yield of tetralin with 0.082 g mL-1 water at
606 K. The gure shows that the yield of tetralin increased with
the reaction time for 5 h. After that, extending the reaction time
This journal is The Royal Society of Chemistry 2009
View Article Online
Fig. 6 Effect of reaction time on naphthalene conversion and the yields
of different compounds (0.082 g mL-1 water, 12.8 mg naphthalene,
0.28 mL formic acid, 6.6 mg catalyst, 606 K).
resulted in a reduction in the yield of tetralin, and the amounts
of coke and decalins increased as the reaction extended from
5 h to 6 h. Therefore, the obvious decrease in the yield of the
tetralin was originated mainly from the deep hydrogenation of
tetralin and the production of more coke. This is understandable
considering the fact that most of the naphthalene could be
converted within 5 h and, therefore, a further increasing in time
resulted in more byproducts.
Effect of the catalyst loading
Fig. 7 displays the dependence of naphthalene conversion
and the yields of different compounds on the amount of
the catalyst used. It can be seen that under the experimental
conditions, the conversion increased with an increase of the
amount of the catalyst up to 6.6 mg. The conversion did not
change with the amount of the catalyst considerably when the
amount of the catalyst exceeded 6.6 mg. However, the yield
of tetralin was reduced slightly. The main reason for this was
that 6.6 mg of catalyst was enough to convert the naphthalene
under the experimental conditions. A further increase of the
catalyst resulted in the production of more coke and the deep
hydrogenated product decalins.
Fig. 7 Effect of catalyst loading on naphthalene conversion and the
yields of different compounds (0.082 g mL-1 water, 12.8 mg naphthalene,
0.28 mL formic acid, 606 K, 5 h).
H/D exchange between naphthalene and D2 O
H/D exchange of some compounds in supercritical or pres-
surized hot deuterium oxide has been conrmed in different
reaction systems.4346 We also studied the naphthalene hydro-
genation in the presence of D2 O with our catalyst. The 2 H NMR
Green Chem., 2009, 11, 10611065 | 1063

spectrum of the reaction mixture after the reaction is presented
in the ESI (Fig. S1). The peaks at 6.87, 2.58 and 1.63 ppm
are assigned to deuterium atoms of the deuterated tetralin, and
those at 7.31 and 7.67 ppm represent deuterium atoms of the
deuterated naphthalene. This suggested that the hydrogen in
water exchanged with the hydrogen in the naphthalene during
the reaction. How this affected the reaction should be studied
further.
Published on 07 May 2009. Downloaded by Michigan State University on 06/08/2013 19:29:21.
Conclusions
The effect of HTW on the hydrogenation reaction of naph-
thalene to produce tetralin was studied using Fe2 (MoO4 )3 as
the catalyst. The results indicated that addition of water could
enhance the yield of tetralin considerably. The maximum yield
of tetralin could reach 85% in the presence of water, while in the
absence of water was only about 60%. The main reason for this
was that the addition of water could suppress the formation of
coke effectively. In other words, the reactant can be used more
effectively in the presence of water. We believe that using water
as a greener additive to enhance the selectivity or yield of the
product may also be applicable to more reactions.
Experimental
Naphthalene was purchased from Shantou Xilong Chemical
Factory (Guangdong, China). Formic acid was provided by
Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). n-
Decane, sulfur (S) powders and n-hexane were obtained from
Beijing Chemical Reagents Company. All the above chemicals
were of analytical grade and used without further purication.
Deuterium oxide was obtained in 99.9% isotopic purity from
Cambridge Isotope Laboratories. Iron molybdenum oxide cat-
alyst Fe2 (MoO4 )3 was prepared using the solgel method.37 The
X-ray diffraction (XRD) pattern was collected on a D/Max 2500
V/PC X-ray diffractometer with high-intensity Cu Ka (40 kV,
200 mA) radiation. The 2 H NMR spectrum was obtained on a
BRUKER AVANCE (600 MHz) NMR spectrometer using CCl4
as the solvent.
All the reactions were carried out in a high pressure
cylindrical-shaped 316 stainless steel reactor of 6.1 mL. In a
typical experiment, a desired amount of naphthalene, catalyst,
S powder (S was essential to activate the catalyst by maintaining
it in the sulded form; the mass ratio of S to catalyst was 6),
water, and formic acid were added into the reactor, and then
the reactor was purged with nitrogen. The loaded reactor was
placed into a preheated isothermal furnace. The reaction time
was recorded from the time when the reactor was placed in the
furnace (about 12 min were required for the reactor to reach
the reaction temperature). After the desired reaction time, the
reactor was taken out of the furnace and cooled in a water
bath to quickly quench the reaction. The cooled reactor was
then opened and the reaction mixture was transferred into a
10 mL vial. The reactor was then triple-rinsed with n-hexane
and the washings were added to the above vial. Then an internal
standard, n-decane, was added into the vial for analysis. The
amounts of tetralin and decalins were determined by an Agilent
4890D gas chromatograph equipped with a SUPELCOWAX-10
capillary column (30 m) and a FID detector. GC-MS analysis
1064 | Green Chem., 2009, 11, 10611065
View Article Online
of the compounds was performed on SHIMADZU-QP2010
equipment.
Acknowledgements
This work was supported by the National Key Basic Research
Project of China (2006CB202503, 2006CB202504) and the
Chinese Academy of Sciences (KJCX2.YW.H16).
Notes and references
1 P. E. Savage, Chem. Rev., 1999, 99, 603621.
2 D. Broll, C. Kaul, A. Kramer, P. Krammer, T. Richter, M. Jung, H.
Vogel and P. Zehner, Angew. Chem., Int. Ed., 1999, 38, 29983014.
3 J. Fraga-Dubreuil and M. Poliakoff, Pure Appl. Chem., 2006, 78,
19711982.
4 J. P. Hallett, P. Pollet, C. L. Liotta and C. A. Eckert, Acc. Chem. Res.,
2008, 41, 458467.
5 K. Prkopsky, B. Wellig and P. R. Rohr, J. Supercrit. Fluids, 2007, 40,
246257.
6 H. Erkonaka, O. O. Soguta and M. Akgun, J. Supercrit. Fluids, 2008,
46, 142148.
7 F. Vogel, M. H. Waldner, A. A. Rouff and S. Rabe, Green Chem.,
2007, 9, 616619.
8 S. Deguchi, K. Tsujii and K. Horikoshi, Green Chem., 2008, 10, 191
196.
9 M. Sasaki Wahyudiono and M. Goto, Chem. Eng. Process., 2008, 47,
16091619.
10 A. A. Galkin, B. G. Kostyuk, V. V. Lunin and M. Poliakoff, Angew.
Chem., Int. Ed., 2000, 39, 27382740.
11 T. Adschiri, Y. Hakuta and K. Arai, Ind. Eng. Chem. Res., 2000, 39,
49014907.
12 B. L. Cushing, V. L. Kolesnichenko and C. J. OConnor, Chem. Rev.,
2004, 104, 38933946.
13 S. Ohara, T. Mousavand, T. Sasaki, M. Umetsu, T. Naka and T.
Adschiri, J. Mater. Sci., 2008, 43, 23932396.
14 M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825835.
15 A. R. Katritzky, D. A. Nichols, M. Siskin, R. Murugan and M.
Balasubramanian, Chem. Rev., 2001, 101, 837892.
16 Y. Ikushima, O. Sato, M. Sato, K. Hatakeda and M. Arai, Chem.
Eng. Sci., 2003, 58, 935941.
17 C. M. Comisar and P. E. Savage, Green Chem., 2004, 6, 227231.
18 A. Laitenen, Y. Takebayashi, I. Kylanlahti, J. YliKauhaluoma, T.
Sugeta and K. Otake, Green Chem., 2004, 6, 4952.
19 S. E. Hunter, C. A. Felczak and P. E. Savage, Green Chem., 2004, 6,
222226.
20 J. B. Dunn and P. E. Savage, Environ. Sci. Technol., 2005, 39, 5427
5435.
21 E. Garcia-Verdugo, J. Fraga-Dubreuil, P. A. Hamley, W. B. Thomas,
K. Whiston and M. Poliakoff, Green Chem., 2005, 7, 294300.
22 J. Fraga-Dubreuil, J. Garcia-Serna, E. Garcia-Verdugo, L. M. Dudd,
G. R. Aird, W. B. Thomas and M. Poliakoff, J. Supercrit. Fluids,
2006, 39, 220227.
23 T. Adschiri, R. Shibata, T. Sato, M. Watanabe and K. Arai, Ind. Eng.
Chem. Res., 1998, 37, 26342638.
24 E. Garcia-Verdugo, Z. M. Liu, E. Ramirez, J. Garcia-Serna, J. Fraga-
Dubreuil, J. R. Hyde, P. A. Hamley and M. Poliakoff, Green Chem.,
2006, 8, 359364.
25 C. Yan, J. Fraga-Dubreuil, E. Garcia-Verdugo, P. A. Hamley, M.
Poliakoff, I. Pearson and A. S. Coote, Green Chem., 2008, 10, 98
103.
26 J. Fraga-Dubreuil, E. Garcia-Verdugo, P. A. Hamley, E. Vaquero, L.
Dudd, I. Pearson, D. Housley, W. Partenheimer, W. B. Thomas, K.
Whistonb and M. Poliakoff, Green Chem., 2007, 9, 12381245.
27 M. Watanabe, T. Sato, H. Inomata, R. L. Smith, K. Arai, A. Kruse
and E. Dinjus, Chem. Rev., 2004, 104, 58035822.
28 S. Hodoshima, H. Nagata and Y. Saito, Appl. Catal., A, 2005, 292,
9096.
29 M. Nuzzi and B. Marcandalli, Fuel Process. Technol., 2003, 80, 23
33.
30 Y. X. Zhao, M. R. Gray and F. Wei, Catal. Lett., 2008, 125, 6975.
This journal is The Royal Society of Chemistry 2009

31 J. S. Yu, B. C. Ankianiec, M. T. Nguyen and I. P. Rothwell, J. Am.
Chem. Soc., 1992, 114, 19271929.
32 T. Kotanigawa, M. Yamamoto and T. Yoshida, Appl. Catal., A, 1997,
164, 323332.
33 S. Albertazzi, G. Busca, E. Finocchio, R. Glockler and A. Vaccari,
J. Catal., 2004, 223, 372381.
34 A. C. A. Monteiro-Gezork, A. Effendi and J. M. Winterbottom,
Catal. Today, 2007, 128, 6373.
35 S. R. Kirumakki, B. G. Shpeizer, G. V. Sagar, K. V. R. Chary and A.
Cleareld, J. Catal., 2006, 242, 319331.
36 K. Ito, Y. Kogasaka, H. Kurokawa, M. Ohshima, K. Sugiyama and
Published on 07 May 2009. Downloaded by Michigan State University on 06/08/2013 19:29:21.
H. Miura, Fuel Process. Technol., 2002, 79, 7780.
37 J. R. Hyde and M. Poliakoff, Chem. Commun., 2004, 14821483.
38 J. R. Hyde, B. Walsh, J. Singh and M. Poliakoff, Green Chem., 2005,
7, 357361.
This journal is The Royal Society of Chemistry 2009
View Article Online
39 W. Kuang, Y. Fan and Y. Chen, J. Colloid Interface Sci., 1999, 215,
364369.
40 M. D. Koretsky, Engineering and Chemical Thermodynamics, John
Wiley & Sons, WileyVCH, 1st edn., 2003, p. 509.
41 V. A. Munoz, S. V. Ghorpadkar and M. R. Gray, Energy Fuels, 1994,
8, 426434.
42 A. Corma, A. Martinez and V. Martines-Soria, J. Catal., 1997, 169,
480489.
43 B. Kuhlmann, E. M. Arnett and M. Siskin, J. Org. Chem., 1994, 59,
53775380.
44 S. Bai, B. J. Palmer and C. R. Yonker, J. Phys. Chem. A, 2000, 104,
5358.
45 B. Kerler, J. Pol, K. Hartonen, M. T. Soderstrom, H. T. Koskela and
M. Riekkola, J. Supercrit. Fluids, 2007, 39, 381388.
46 Z. Tian, L. Lis and S. R. Kass, J. Am. Chem. Soc., 2008, 130, 89.
Green Chem., 2009, 11, 10611065 | 1065