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Catalysis Communications 9 (2008) 13601363

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Production of 1,3-propanediol by hydrogenolysis of glycerol

catalyzed by Pt/WO3/ZrO2
Tadahiro Kurosaka a, Hideyuki Maruyama b, Ikuya Naribayashi b, Yoshiyuki Sasaki a,*
a

Advanced Industrial Science and Technology, Biomass Technology Research Center, 2-2-2, Hiro-suehiroKure, Hiroshima 737-0197, Japan
b
Sakamoto Yakuhin Kogyo Co. Ltd., 1-20 Rinkaicho, Izumiotsu City, Osaka 595-0075, Japan
Received 15 September 2007; received in revised form 23 November 2007; accepted 28 November 2007
Available online 4 December 2007

Abstract
Glycerol hydrogenolysis was catalyzed by Pt/WO3/ZrO2 to give 1,3-propanediol (1,3-PD) in the yields up to 24%. The catalytic activities and the selectivity toward 1,3-PD were remarkably aected by the type of support, loaded noble metal (NM) and the preparation/
impregnation procedure. Controlled experiments show that the active site of catalyst for the formation of 1,3-PD may be the Pt over
WO3 supported on ZrO2.
2007 Elsevier B.V. All rights reserved.
Keywords: 1,3-Propanediol; Glycerol; Hydrogenolysis; Noble metal; Tungsten oxide

1. Introduction
1,3-PD is a valuable chemical used in the synthesis of
polymethylene terephthalates and in the manufacture of
polyurethanes and cyclic compounds [1,2]. Polymers based
on 1,3-PD exhibit many special properties such as good
light stability, biodegradability, and improved elasticity.
1,3-PD is currently produced from petroleum derivatives
such as ethylene oxide (Shell route) or acrolein (DegussaDuPont route) by chemical catalytic routes [3]. On the
other hand, glycerol is a major byproduct of the biodiesel
industry; approximately 1 ton of a crude glycerol is formed
for every 10 tons of biodiesel produced [4]. The surging
demands for renewable energy sources including biodiesel
may oer opportunities for such new applications of glycerol as its conversion to added-value products, and this
may contribute to the improvement of the economical viability of the biodiesel production itself [5].
In this context, much attention has been focused on the
development of eective methods for the production of 1,3*

Corresponding author. Tel.: +81 823 72 1940; fax: +81 823 72 1970.
E-mail address: y.sasaki@aist.go.jp (Y. Sasaki).

1566-7367/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.11.034

PD from glycerol. Relatively well developed is the fermentation method using bacterial strains in which glycerol is
converted to 1,3-PD in good yields (>70%), but the reaction proceeds very slowly in water solution and in two steps
[613]. On the other hand, the direct hydrogenolysis of
glycerol to 1,3-PD is particularly interesting because it
may be produced in organic solvents and in one step. So
far, Bullock et al. reported that the dehydroxylation of
glycerol occurred with homogeneous ruthenium catalysts
in sulfolan [14]. This reaction proceeds under mild conditions (5.2 MPa, 110 C), though the yield of 1,3-PD
remains very low (<3%). Tomishige et al. reported that
the combination of an active carbon-supported Ru catalyst
with a cation exchange resin (Amberlyst 15) showed a high
level of activity during the hydrogenolysis of glycerol
[15,16]. However, 1,2-propanediol (propylene glycol,
1,2-PD) was predominantly formed, while the yield in
1,3-PD remained very low (<0.4%). They also discussed
the reaction mechanism over Ru/C + Amberlyst 15 catalysts. The dehydration of glycerol to acetol is catalyzed
by the acid catalysts. The subsequent hydrogenation of
acetol on the metal catalysts gives 1,2-PD. And the OH
group on Ru/C can also catalyze the dehydration of

T. Kurosaka et al. / Catalysis Communications 9 (2008) 13601363

glycerol to 3-hydroxypropionaldehyde, which can then be

converted to 1,3-PD and the other degradation products
through subsequent hydrogenation. Furthermore, Chaminand et al. reported that H2WO4 was eective in enhancing
glycerol conversion and the best result was obtained by
using sulfolane as solvent; 1,3-PD was formed in 4% [3].
Therefore, the attempts so far reported show that the
reaction conditions favorable for the formation of 1,3-PD
involve the presence of solid acids such as tungsten oxide,
noble metals, and polar aprotic solvents such as sulfolane.
Based on this knowledge, several noble metal types were
prepared on tungsten oxide-supported catalysts. The
catalytic activity of these noble metal types were examined
for the hydrogenolysis of glycerol. DMI (1,3-dimethyl2-imidazolidinone) was used as solvent, because it was considered more stable than sulfolane under the reaction
conditions.
2. Experimental
The supported tungsten oxide catalysts (WO3: 20 wt%)
were prepared by impregnation method using a (NH4)6(H2W12O40)
nH2O solution. AlMCM-41, SiO2Al2O3,
Al2O3, TiO2 (Anatase type), HY, and ZrO2 were used as
a support. AlMCM-41, SiO2Al2O3, Al2O3, and TiO2 were
purchased from SigmaAldrich and used as received. HY
was purchased from Wako Chemicals, Ltd. Zirconium
hydroxide, Zr(OH)4 was obtained by hydrolyzing ZrOCl2
with aqueous ammonia added until the solution reached
pH 8.0, followed by washing and then drying at
373 K for 24 h. The catalysts were calcined at 773 K for
3 h in air.
The noble metal (NM) was then loaded on supported
tungsten oxide catalysts at 2 wt% based on the NM by
the impregnation method using H2PtCl6
6H2O, RhCl,
PdCl2, RuCl, ReCl, and IrCl4 as their precursors. Pt/
WO3 catalyst was similarly prepared but using tungsten
oxide as support. PtWO3/ZrO2 catalyst was prepared by
co-impregnation using a H2PtCl6
6H2O solution and a
(NH4)6(H2W12O40)
nH2O solution. The resulting solids
were dried at 373 K and calcined at 773 K for 3 h in air.
The hydrogenolysis of glycerol was carried out in a 10mL-stainless steel autoclave. After the autoclave was
charged with glycerol (3 mmol), DMI (0.2 mL), and catalyst (0.1 g) and purged with H2, hydrogen was introduced
at the initial pressure of 8.0 MPa. Then the autoclave was
heated to the reaction temperature (443 K) which was
maintained for the entire reaction time of 18 h.
The products were identied by GCMS (Shimadzu QP5050 with FFAP capillary column) and analyzed by GC
(Shimadzu GC-14B with FFAP capillary column for liquid
products, GL sciences GC 353B with RT-QPLOT capillary
column for gas products) equipped with FID. The unreacted glycerol and diglycerol were analyzed by HPLC (Jasco LC-2000 with AminexHPX-87X column). An internal
standard method using n-butanol was employed to calculate the product yields for both GC and HPLC.

1361

X-ray diraction (XRD) of the catalysts was recorded

on an X-ray diractometer (Rigaku Co., Cu Ka, 40 kV,
20 mA).
3. Results and discussion
The eect of the supports loaded with tungsten oxide
were rstly examined and then with platinum for the
hydrogenolysis of glycerol in DMI at 443 K. The results
are listed in Table 1.
The predominant products were 1,3-PD, 1,2-PD, and npropanol (n-PrOH). The catalytic activity signicantly varied with the type of support, but all the catalysts tested outperformed those previously reported in terms of the yield
of 1,3-PD. The best result so far was obtained with Pt/
WO3/ZrO2; 1,3-PD was formed in the yield of 24.2% and
twice the selectivity of 1,2-PD. However, a signicant
amount of n-PrOH was formed with this catalyst, probably
because of the severe reaction conditions. iso-PrOH, ethanol, diglycerol, propane, ethane and methane were the
other minor products analyzed upon which ca. 10% was
the total yield.
The results of XRD analyses of these catalysts are
shown in Fig. 1a,b. No peak of Pt metal nor tungsten oxide
was observed in the case of Pt/WO3/ZrO2, Pt/WO3/Al2O3,
and Pt/WO3/SiO2Al2O3, all of which gave high yields of
1,3-PD (>11%) with high glycerol conversion (>40%). On
the other hand, small peak of Pt metal and small peaks
of WO3 were observed in the XRD analyses of Pt/WO3/
AlMCM-41, Pt/WO3/HY, and Pt/WO3/TiO2, all of which
gave the relatively low yields in 1,3-PD (<8%). This trend
of result indicates the importance of the high dispersion
of WO3 and Pt on the supports for the eective hydrogenolysis of glycerol.
The type of NM loaded on the zirconia supported tungsten oxide catalysts also greatly aects the hydrogenolysis
of glycerol as shown in Table 2.
Pt and Rh gave much higher glycerol conversions compared with other NMs, but the yield of 1,3-PD remained
low with Rh. Since almost similar XRD patterns were
observed among the NM/WO3/ZrO2 catalysts; no peaks
Table 1
Eect of the supported tungsten oxide catalysts modied by Pta
Catalystsb

Pt/WO3/TiO2
Pt/WO3/HY
Pt/WO3/AlMCM-41
Pt/WO3/SiO2Al2O3
Pt/WO3/Al2O3
Pt/WO3/ZrO2

Yield (%)
1,3-PD

1,2-PD

n-PrOH

Glycerol

6.5
7.2
7.5
11.0
13.2
24.2

7.1
8.9
7.0
11.6
11.0
12.5

5.1
5.0
7.1
9.5
11.6
27.5

83.1
74.1
72.2
57.8
56.1
14.2

a
Reaction conditions: glycerol: 3 mmol; DMI: 0.2 mL; initial H2 pressure: 8.0 MPa; reaction time: 18 h; catalyst: 100 mg (Pt 2 wt%, WO3 19.6
wt%); reaction temperature: 443 K.
b
No product was obtained in the hydrogenolysis of glycerin without any
catalyst; 97% of glycerol used was recovered.

1362

T. Kurosaka et al. / Catalysis Communications 9 (2008) 13601363

Intensity

Table 3
Eect of the preparation method and the components of catalysta

Pt/WO3/ZrO2

Pt/WO3/Al2O3
Pt/WO3/SiO2-Al2O3
10

20

30

40
2/degree

50

60

70

Intensity

WO3(020)
Pt(111)
Pt/WO3/TiO2

Pt/WO3/HY
Pt/WO3/AlMCM-41
10

20

30

40
2/degree

50

60

70

Fig. 1. XRD patterns of supported tungsten oxide catalysts modied by

Pt. (After calcination at 773 K for 3 h.)

Table 2
Eect of the NM loaded on WO3/ZrO2 catalysta
Catalyst

Pt/WO3/ZrO2
Pd/WO3/ZrO2
Rh/WO3/ZrO2
Ru/WO3/ZrO2
Ir/WO3/ZrO2

Yield (%)
1,3-PD

1,2-PD

n-PrOH

Glycerol

Pt/WO3/ZrO2
Pt/WO3
Pt/ZrO2
WO3/ZrO2
Pt/ZrO2 + WO3/ZrO2
PtWO3/ZrO2

24.2
3.0
2.2
2.6
2.8
6.5

12.5
7.2
3.0
2.7
4.6
6.7

27.5
2.0
3.1
2.8
5.8
6.4

14.2
83.6
93.8
88.5
80.5
78.8

WO3(200)

WO3(001)

Catalysts

Yield (%)
1,3-PD

1,2-PD

n-PrOH

Glycerol

24.2
4.7
4.1
3.4
3.1

12.5
6.6
28.2
9.1
6.7

27.5
4.8
22.7
8.1
3.4

14.2
76.0
13.6
53.3
78.2

Reaction conditions: glycerol: 3 mmol; DMI: 0.2 mL; initial H2 pressure: 8.0 MPa; reaction time: 18 h; catalyst: 100 mg (NM 2 wt%, WO3
19.6 wt%); reaction temperature: 443 K.

of noble metals or tungsten oxide were observed, it is considered that the dispersions of NMs are not responsible for
the dierence in their catalytic activities but the type of NM
itself. This result suggests that Pt does not only work as an
active site for the hydrogenation of possible intermediates
such as 3-hydroxypropionaldehyde derived from glycerol
but is also concerned with the initial step of its decomposition to some form of intermediate.
In order to conrm this assumption, several catalysts
consisting of Pt, WO3 and/or ZrO2 were prepared and
tested (Table 3).
The catalytic activity of Pt/WO3 was not so high as
that of Pt/WO3/ZrO2 probably because of the low acidity
of WO3 compared with WO3/ZrO2. Neither Pt/ZrO2 nor
WO3/ZrO2 was a good catalyst for the conversion of glyc-

Reaction conditions: glycerol: 3 mmol; DMI: 0.2 mL; initial H2 pressure: 8.0 MPa: reaction time: 18 h; catalyst: 100 mg; reaction temperature:
443 K.
b
Pt/ZrO2 and WO3/ZrO2: 100 mg each.

erol. Furthermore, no great improvement was observed

even when these catalysts were used in combination. These
results together with the low catalytic activity of PtWO3/
ZrO2 suggest that the reaction mechanism including the
glycerol activation on WO3 over ZrO2 and the subsequent
hydrogenation of the resulted intermediate on Pt over
ZrO2 is not plausible. Thus, it can be concluded that Pt/
WO3/ZrO2 is not a mere bi-functional catalyst in which
its acid sites and Pt metal sites play separate roles but
may contain active sites for the activation of glycerol
itself.
On the basis of the proposed active site consisting of
Pt, WO3, and ZrO2, it would be possible to develop better
catalysts for the hydrogenolysis of glycerol to 1,3-PD.
Additional studies are underway concerning the dierent
methods for the preparation of Pt/WO3/ZrO2 catalysts
and the way of suppressing the further hydrogenolysis of
PDs to PrOH and the other degradation products.
4. Conclusions
Glycerol hydrogenolysis was catalyzed by Pt/WO3/ZrO2
to give 1,3-PD in high yields up to 24%. The other noble
metals tested for this catalysis were much less eective for
the formation of 1,3-PD than Pt. Furthermore, a sequential
impregnation of WO3 and then Pt on ZrO2 is necessary to
make eective catalysts; the other preparation such as
simultaneous impregnation or separate application of each
components resulted in poor catalytic activity. These
results suggest that the active site for the hydrogenolysis
of glycerol to 1,3-PD may be Pt on WO3 supported on
ZrO2.
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