Catalysis Communications 11 (2010) 620–623

Contents lists available at ScienceDirect

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

Selective conversion of glycerol to acetol over sodium-doped metal oxide catalysts

Anil K. Kinage a,1, Pravin P. Upare a,b, Palraj Kasinathan a,b, Young Kyu Hwang a,b,*, Jong-San Chang a,b,*
a
Catalysis Center for Molecular Engineering (CCME), Korea Research Institute of Chemical Technology (KRICT), Shinseongno 17, Yusung, Daejeon 305-600, Republic of Korea
b
School of Science, University of Science and Technology (UST), 113 Gwahangno, Youeong-gu, Daejeon 305-333, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Glycerol conversion to produce 1-hydroxypropan-2-one (acetol) has been investigated over 5 wt.% Na-
Received 13 November 2009 doped on CeO2, Al2O3, ZrO2 and Ga2O3. The observed performance demonstrates that the 5 wt.% Na-doped
Received in revised form 24 December 2009 CeO2 is one of the best catalysts to exhibit high conversion and high selectivity for acetol formation
Accepted 5 January 2010
among catalysts tested in this work. XRD patterns of Na-doped catalysts showed that no alteration of
Available online 11 January 2010
metal oxide phases was observed after sodium doping. Temperature-programmed desorption (TPD) of
CO2 and NH3 show the optimum number of base and acid sites on 5 wt.% Na-doped CeO2.
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Glycerol conversion
Acetol
Na loaded metal oxide catalysts
Continuous fix bed reactor

1. Introduction as high temperatures and high pressures of reaction, low pro-

Reaction of vegetable oil with methanol to create fatty acid
methyl esters (FAME) as biodiesel fuel has received considerable
attention because it is derived from renewable resources [1–5].
Glycerol was a by-product of making soap and oleochemicals,
however, today close to two-thirds of world glycerol production
comes from biodiesel. The combine US and European output of
glycerol last year was almost triple than it was in 2004. This
makes glycerol a particularly interesting molecule for the syn-
thesis of other valuable chemical products. Recently, a number
of review articles are published for converting glycerol into value
added chemical products [6–8]. Catalytic conversion of glycerol
by hydrogenolysis to 1,2-propanediol (or propylene glycol) could
be one of the industrial important routes for using glycerol re-
sources and could offer a sustainable alternative to the current
production of 1,2-propanediol based on propylene oxide [9,10].
1,2-Propanediol is not only a valuable chemical but also a start-
ing compound for the production of polymers. The hydrogenoly-
sis of glycerol to 1,2-propanediol generally proceeds via two
steps; in first step glycerol to 1-hydroxypropan-2-one (acetol)
and in second step hydrogenation of acetol to 1,2-propanediol
[11–15]. However, these processes are inappropriate to commer-
cialize due to common drawbacks of existing technologies such
duction efficiency due to use of dilute solution of glycerol and
low selectivity for 1,2-propanediol. Therefore, these problems
will be overcome if glycerol can be converted to acetol in first
step, and then by further hydrogenation of acetol in second step
to produce 1,2-propanediol. Nevertheless, conversion of glycerol
to acetol has received adequate attention and few studies re-
ported synthesis of acetol in semi-batch reactor by reactive dis-
tillation setup [16] under reduced pressure using vacuum,
noncatalytic conversion at high temperature liquid water and
high pressure carbon dioxide [17] and low pressure packed
bed gas phase conversion using very dilute feed of glycerol
[18]. Therefore, developing proper fixed bed continuous flow
process operated at desired temperature and atmospheric pres-
sure for conversion of glycerol to acetol reaction still remains
an open challenge.
In this work, we report a continuous process to convert glycerol
into acetol using sodium-doped metal oxide catalyst. To the best of
our knowledge, there is no report for the utilization of continuous
fixed bed process to convert glycerol into acetol using sodium-
doped metal oxide catalysts. It is supposed that the reported pro-
cess will find its use in commercial production of 1,2-propanediol
via hydrogenation of acetol.

2. Experimental
* Corresponding authors. Tel.: +82 42 860 7680; fax: +82 42 860 7676 (Y.K.
Hwang), tel.: +82 42 860 7673; fax: +82 42 860 7676 (J.-S. Chang).
2.1. Chemicals
E-mail addresses: ykhwang@krict.re.kr (Y.K. Hwang), jschang@krict.re.kr (J.-S.
Chang).
1
Present address: Catalysis and Inorganic Chemistry Division, National Chemical Cerium nitrate (Sigma–Aldrich), aluminum nitrate (Sigma–Al-
Laboratory, Dr. Homi Bhabha Road, Pashan Pune-411008, India. drich), zirconyl nitrate (Fluka), gallium nitrate (Sigma–Aldrich),

1566-7367/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2010.01.008
 A.K. Kinage et al. / Catalysis Communications 11 (2010) 620–623 621

sodium hydroxide (Sigma–Aldrich) and glycerol (99% Sigma–Al-
drich) were used without further purification for the synthesis of
the catalysts.
2.2. Catalyst preparation
Sodium loaded catalysts were prepared by following method.
First nitrate salts of metal precursor were converted into their
hydroxide forms by adding it to deionized water and precipi-
tated by the drop wise addition of 0.5 M sodium hydroxide.
Respective hydroxides were recovered by filtration, washing
and drying. On these dried hydroxides sodium was doped by
wet impregnation and then calcined at 700 °C for 5 h. The calci-
nations condition is chose from the earlier report [19]. The
amount of sodium hydroxide and metal hydroxide was adjusted
to prepare the catalysts supported with 5 wt.% of Na. In wet
impregnation technique no sodium loss can occurs during calci-
nations, therefore, it is assume that all sodium is present in the
catalyst after calcinations. From XRD analysis confirmed the for-
mation of catalyst and by using Scherrer formula, the particle
size of the catalysts 5 wt.% Na/CeO2, 5 wt.% Na/Al2O3, 5 wt.%
Na/ZrO2 and 5 wt.% Na/Ga2O3, was found to be 20–25 nm, 5–
8 nm, 15–20 nm and 27–33 nm, respectively.
2.4. Glycerol conversion
Glycerol conversion was carried out in a fixed bed continuous
flow reactor (stainless steel 316, OD 3/8 inch, thickness 0.035 inch)
equipped with vaporizer. The reactor temperature was controlled
by an electric furnace at constant temperature. The time-on-
stream activity of glycerol conversion reaction at different temper-
ature (250–400 °C), at different concentration of glycerol in feed
and at different WHSV was carried out at atmospheric pressure
for 24 h. The space velocity of glycerol, WHSV (weight-hourly
space velocity, g of glycerol fed per g of catalyst per hour) was
maintained by controlling the concentration of glycerol. The reac-
tant (diluted glycerol with deionized water), without further puri-
fication, was continuously fed by using liquid syringe pump having
flow controllers. The conversion of glycerol was determined by
analyzing periodically the composition of the stream, after con-
densing liquid products, by using a gas chromatograph (GC)
equipped with a flame ionization detector (FID) and DB wax col-
umn (J&W SCIENTIFIC, 30 m  0.53 mm). The mass balance was
calculated by measuring the condensing liquid products and the
feed.
3. Results and discussion

2.3. Characterization Fig. 1 shows results on time-on-stream activity and product

Na-doped catalysts (5 wt.%) were characterized by XRD, tem-
perature-programmed desorption of CO2 and ammonia adsorption.
Powder X-ray diffraction patterns of all the samples were obtained
by a Rigaku diffractometer (D/MAX IIIB, 2 kW) using Ni-filtered Cu
Ka-radiation (40 kV, 30 mA, k = 1.5406 Å) and a graphite crystal
monochromator. The CO2 and ammonia adsorption and desorption
isotherms were obtained by chemisorption analyzer (Model: Auto-
chem 2920, Micromeritics, USA) using 10% CO2 in He and 15%
ammonia in He, respectively.
selectivity of glycerol conversion over 5 wt.% Na/CeO2, 5 wt.% Na/
Al2O3, 5 wt.% Na/ZrO2 and 5 wt.% Na/Ga2O3, catalysts at 350 °C
for 24 h. After 24 h of time-on-stream, the glycerol conversion is
in the order of 5 wt.% Na/CeO2 > 5 wt.% Na/Al2O3 > 5 wt.% Na/
Ga2O3 > 5wt.% Na/ZrO2. The high conversion and selectivity of ace-
tol was obtained over 5 wt.% Na/CeO2. In all the catalyst the glyc-
erol conversion decreases initially up to 8 h and then becomes
stable. Interestingly, the conversion over 5 wt.% Na/ZrO2 and
5 wt.% Na/Ga2O3 is low (less than 10% at 6 h of time-on-stream).

80
Product selectivity

70
90 Propanol
80 60
(mole %)

Allyl alcohol
Acetol selectivity

70 50 Acetol
60 Propanic acid
(mole %)

40
50 1,2 Propane diol
30 Ethylene glycol
40
30 20
20 10
10
90
Glycerol conversion
Glycerol conversion

70 5 wt % Na/CeO2 80
60 5 wt % Na/Al2O3 70
(mole %)
(mole %)

50 5 wt % Na/ZrO2 60
40 5wt % Na/Ga2O3 50
40
30
30
20
20
10
10
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Time-on-stream (h) Time-on-stream (h)
Fig. 1. Time-on-stream activity and acetol selectivity in glycerol conversion over Fig. 2. Time-on-stream activity and product selectivity in glycerol conversion over
Na-doped metal oxide catalysts at 350 °C. 5 wt.% Na/CeO2 at 350 °C.
622 A.K. Kinage et al. / Catalysis Communications 11 (2010) 620–623

OH OH OH
-H2 -H2O +H2 O
HO OH O OH O
Basic sites HO

O +H2 OH
OH + O HO

O + O CO + H2
-H2O
HO OH O OH

3-hydroxypropanal O
HO
OH OH O
-H2O
HO OH HO HO
Acidic sites

Scheme 1. Possible reaction pathways for acetol formation on acid and basic sites of Na-doped catalysts.

Table 1
A fte r re a ctio n Acid–base properties of Na-doped metal oxide catalysts and their catalytic properties
for acetol formation.

Catalyst No. of No. of Ratio of basicity/ Acetol

(d ) acid sites base sites acidity selectivity
(mmol g 1)a (mmol g 1)b (%)c
Na/CeO2 3.8 8.1 2.1 68.6
(c) Na/Al2O3 9.9 35.8 3.6 57.3
Na/Ga2O3 4.1 13.4 3.2 35.2
(b ) Na/ZrO2 4.9 14.2 2.9 49.8
Intensity (a.u.)

a
Number of acid sites measured by NH3-TPD.
b
Number of base sites measured by CO2-TPD.
c
(a ) Acetol selectivity at 10% glycerol conversion.

B e fo re re a c tio n
10 20 30 40 50 60
2 θ /degree
Fig. 3. XRD powder pattern for (a) 5 wt.% Na/ZrO2, (b) 5 wt.% Na/Ga2O3, (c) 5 wt.%
Na/Al2O3, and (d) 5 wt.% Na/CeO2 before and after reaction.
The selectivity for acetol after 6 h of reaction is slightly in-
creases in the order of 5 wt.% Na/CeO2 > 5 wt.% Na/Al2O3 > 5 wt.%
Na/ZrO2 > 5 wt.% Na/Ga2O3 which is in line with the order of de-
crease in the glycerol conversion over the catalysts. The product
selectivity and glycerol conversion is presented in Fig. 2. The re-
sults show high selectivity towards acetol formation. The selectiv-
ity of acetol formation generally increases with decreasing
conversion of glycerol. The other side products formed in the reac-
tion was due to cracking; further dehydration of acetol, and/or
hydrogenolysis is represented in Scheme 1.
It is hard to explain why the 5 wt.% Na/CeO2 shows the best
performance among the catalysts, so the catalysts were character-
ized by using XRD and temperature-programmed desorption of
ammonia and CO2 methods. Fig. 3 shows the XRD patterns of
5 wt.% Na-doped on ZrO2, Ga2O3, Al2O3 and CeO2 supports. The re-
(d )
sults suggest the zirconia calcined at 700 °C show monoclinic
phase for ZrO2. Earlier it was also observed that zirconia calcined
(c ) at higher temperature (>500 °C) shows monoclinic phase [19].
The other phases observed were Ga2O3, Al2O3 and CeO2 phases.
The XRD pattern shows Na-doping on Ga2O3, Al2O3 and CeO2 sup-
(b )
port cannot modify the phases of Ga2O3, Al2O3 and CeO2 supports.
Table 1 shows the acidity and basicity of the Na-doped on ZrO2,
Ga2O3, Al2O3 and CeO2 supports. The results shows that Na/CeO2
(a ) has less acidic and basic sites compare to other three catalysts.
The basicity to acidity ratio in Na/CeO2 is 2.1, which is less than
70 80 90 the other catalyst. The selectivity of acetol formation is higher in
case of Na/CeO2 catalyst. This clearly shows that the optimum
number of acidity and basicity gives higher selectivity in case of
Na/CeO2. The other catalysts having more basic site leads more al-
lyl alcohol and cracking of the intermediate leads to formation of
CO and H2 as by-products. The Scheme 1 shows the proposed
mechanism for formation of acetol over acidic and basic sites. On
acidic site first dehydration of glycerol occur followed by selective
acetol formation. However, over basic site first dehydrogenation of
glycerol occur followed by dehydration of glycerol leading acetol.
The large amount of acidic sites on catalyst gives secondary reac-
tion product as 3-hydroxypropanal, which is unstable at reaction
condition [20] and leads formation of allyl alcohol and cracking
leads formation of CO and H2 as by-product of reaction as shown
in Scheme 1. However, excess basic site give further cracking of
acetol and formation of ethylene glycol as by-product of the reac-
tion [21,22]. Therefore, we conclude that optimum number of
acidic and basic sites is needed for selectively formation of acetol.
Na/CeO2 shows ratio 2.1 for basic to acidic site and which may be
more suitable to obtain higher selectivity of acetol formation.
 A.K. Kinage et al. / Catalysis Communications 11 (2010) 620–623 623

90 and unstable intermediate product of glycerol dehydrogenation

80 leads by-product formation as shown in Scheme 1. To understand
Acetol selectivity

the effect of glycerol concentration on the conversion and acetol

70 selectivity the reaction is carried out using different concentration
(mole %)

60 of glycerol in the feed. As shown in Fig. 5, the glycerol conversion in-

50 creases and acetol selectivity decreases with decreasing concentra-
40 tion of glycerol in feed. At lower concentration decrease in
selectivity of acetol formation is attributed to more side reactions
30
forming undesired products. However, at 12% glycerol concentration
20 in feed shows higher selectivity for acetol formation. This may be due
10 to the optimum contact time needed for the formation of acetol. The
increase glycerol conversion with decreasing concentration of glyc-
100 250°C erol in feed is may be because of the increase in contact time and
Glycerol Conversion

300°C therefore, decreases the selectivity of acetol formation.

80 350°C
400°C
(mole %)

60 4. Conclusions

40 Glycerol to selective acetol formation has been investigated

over sodium-doped metal oxide catalysts in order to find efficient
20 catalyst for the production of acetol. The 5 wt.% Na-doped CeO2
catalyst prepared by co-precipitation followed by calcination at
0 700 °C shows very high glycerol conversion with high selectivity
for acetol compared to 5 wt.% Na-doped ZrO2, Ga2O3, and Al2O3.
0 5 10 15 20 25
The sodium loading does not alter the phases of support metal
Time-on-stream (h)
oxide. The remarkable performance of Na/CeO2 catalyst is observed
Fig. 4. Effect of reaction temperature on time-on-stream activity and acetol because of the optimum number of acidic and basic sites of Na/
selectivity in glycerol conversion over 5 wt.% Na/CeO2. CeO2 catalyst.

90
Acknowledgements
80
Acetol selectivity

70 This work was supported by Institutional Research Program of

(mole %)

60 KRICT. Additional support for this work came from Ministry of

50 Knowledge Economy (TS091-49). The authors thank Mr. Jeong Ho
Lee for his helpful discussion. Dr. Anil K. Kinage acknowledges
40
KOFST for awarding the visiting scientist fellowship under Brain
30 Pool program at KRICT.
20
10 References
100
Feed 3% [1] D.L. Klass, Biomass for Renewable Energy, Fuels and Chemicals, Academic
Glycerol conversion

90 Feed 6 % Press, San Diego, 1998. p. 1.

80 Feed12 % [2] M. Canakci, J.V. Gerpen, Trans. ASAE 44 (2001) 1429.
[3] G.J. Suppes, M.A. Dasari, E.J. Doskocil, P.J. Mankidy, M.J. Goff, Appl. Catal. A:
(mole %)

70 Feed 25 %
Gen. 257 (2004) 231.
60 [4] C.-W. Chiu, M.J. Goff, G.J. Suppers, AIChE 144 (2005) 1274.
50 [5] A. Behr, J. Eiting, K. Irawadi, J. Leschinski, F. Linder, Green Chem. 10 (2008) 13.
[6] D.T. Johnson, K.A. Taconi, AIChE J. 26 (2007) 338.
40 [7] C.-H. Zhou, J.N. Beltramini, T.-X. Fan, G.Q. Lu, Chem. Soc. Rev. 37 (2008) 527.
30 [8] J.M. Kenar, Lipid Technol. 19 (2007) 249.
20 [9] A.E. Martin, F.H. Murphy, Kirk–Othmer Encyclopedia of Chemical Technology,
fourth ed., vol. 17, John Wiley & Sons, Inc., New York, 1994. p. 715.
10 [10] D.T. Trent, Kirk–Othmer Encyclopedia of Chemical Technology, fourth ed., vol.
0 20, John Wiley & Sons, Inc., New York, 1996.
0 5 10 15 20 25 [11] M.A. Dasari, P.-P. Kiatsimkul, W.R. Sutterlin, G.J. Suppes, Appl. Catal. A: Gen.
281 (2005) 225.
Time-on-stream (h) [12] T. Miyazawa, Y. Kusunoki, K. Kunimori, K. Tomishige, J. Catal. 240 (2006) 213.
[13] T. Miyazawa, S. Koso, K. Kunimori, K. Tomishige, Appl. Catal. A: Gen. 329
Fig. 5. Effect of different concentration of glycerol feed on time-on-stream activity (2007) 30.
and acetol selectivity in glycerol conversion reaction over 5 wt.% Na/CeO2 at 350 °C. [14] S. Wang, H. Liu, Catal. Lett. 117 (2007) 62.
[15] E.P. Maris, W.C. Ketchie, M. Murayama, R.J. Davis, J. Catal. 251 (2007) 281.
[16] C.-W. Chiu, M.A. Dasari, G.J. Suppes, W.R. Suttterlin, AIChE J. 52 (2006) 3543.
The effect of reaction temperature on the glycerol conversion [17] A. Yamaguchi, N. Hiyoshi, O. Sato, C.V. Rade, M. Shirai, Chem. Lett. 37 (2008)
and selectivity of acetol was studied over Na/CeO2 catalyst and 926.
[18] C.-W. Chiu, A. Tekeei, W.R. Sutterlin, J.M. Ronco, G.J. Suppes, AIChE J. 54 (2008)
the result is shown in Fig. 4. As shown in Fig. 4, the conversion of 2456.
glycerol increases and acetol selectivity decreases with increasing [19] M.M. Devassv, S.B. Halligudi, J. Mol. Catal. A: Chem. 253 (2006) 8.
reaction temperature from 250 to 350 °C. However, at 400 °C selec- [20] S.-H. Chai, H.P. Wang, Y. Liang, B.Q. Xu, Green Chem. 9 (2007) 1130.
[21] D.K. Sohounloue, C. Montassier, J. Barbier, React. Kinet. Catal. Lett. 22 (1983) 391.
tivity of acetol formation decreased compare to 350 °C. It may be [22] C. Montassier, J.C. Menezo, L.C. Hoang, C. Renaud, J. Barbier, J. Mol. Catal. 70
because of at higher temperature (350 °C) cracking of glycerol (1991) 99.