Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts

Zhenle Yuan
a
, Junhua Wang
a
, Lina Wang
b
, Weihui Xie
b
, Ping Chen
a,
**
, Zhaoyin Hou
a,
*
, Xiaoming Zheng
a
a
Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou 310028, China
b
Key Laboratory of Advanced Textile Materials and Manufacturing Technology (Zhejiang Sci-tech University), Hangzhou 310012, China
a r t i c l e i n f o
Article history:
Received 12 January 2010
Received in revised form 5 April 2010
Accepted 8 April 2010
Keywords:
Biodiesel
Glycerol
Hydrogenolysis
1,2-Propanediol
Catalysts
a b s t r a c t
Hydrogenolysis of biodiesel derived glycerol to 1,2-propanediol (1,2-PDO) has attracted much attention
in recent years. In this work, glycerol hydrogenolysis to 1,2-PDO was performed over CuO/MgO catalysts
prepared by impregnation and coprecipitation at 180 C and 3.0 MPa H
2
. It was found that the Cu(15)/
MgO catalyst prepared by coprecipitation had the best activity. The conversion of glycerol and the selec-
tivity of 1,2-PDO over Cu(15)/MgO reached 72.0% and 97.6%, respectively. And the conversion of glycerol
was further increased to 82.0% when small amount of NaOH was added in the reaction mixture. Those
highly active catalysts were characterized by X-ray diffraction, transmission electron microscopy,
N
2
-adsorption and temperature-programmed reduction with H
2
. Characterization results revealed that
the activity of the prepared catalysts depended strongly on the particle sizes of both Cu and MgO. Cata-
lysts that have smaller sized Cu and MgO particles are more active for glycerol hydrogenolysis.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
In the production of biodiesel via transesterication of triglycer-
ides with methanol, about 1 kg of crude glycerol is formed as a by-
product for every 9 kg of biodiesel (Karinen and Krause, 2006).
Glycerol production averages more than 350,000 tons per year in
the United States and it has tripled within the past 10 years in
Europe. Current disposal of surplus glycerol is used for producing
energy by incineration (Slinn et al., 2008; Atia et al., 2008). One
concern regarding to biodiesel production is how to do with this
by-product. Thus, producing value-added chemicals from glycerol
instead of incineration is of great importance in both environmen-
tal protection and economic benet.
Recently, it was reported that this surplus biodiesel derived
glycerol could be utilised as a renewable feedstock for replacing
fossil-derived chemicals. Catalytic conversion of glycerol to value-
added chemicals such as acrolein (Watanabe et al., 2007; Tsukuda
et al., 2007), glyceric acid (Demirel et al., 2007; Dimitrations
et al., 2006; Gao et al., 2009; Liang et al., 2009) and propanediols
(1,2-PDO, 1,3-PDO) are of great importance. In latest years, much
attention has been paid to catalytic hydrogenolysis of glycerol to
1,2-PDO (Alhanash et al., 2008; Chaminand et al., 2004; Dasari
et al., 2005; Feng et al., 2007, 2008; Furikado et al., 2007; Maris
et al., 2007; Maris and Davis, 2007; Miyazawa et al., 2006a,b,
2007; Montassiera et al., 1991; Perosa and Tundo, 2005; Wang
and Liu, 2007), these achievements were well summarized in recent
published works (Behr et al., 2008; Pagliaro et al., 2007; Zhou et al.,
2007). It is popularly suggested that the mechanism of glycerol
hydrogenolysis to 1,2-PDO varies in different reaction mediums.
In acidic conditions, glycerol hydrogenolysis undergoes in two
separated steps, in which glycerol rstly dehydrates to acetol (cat-
alyzed by acid active sites) and then the formed acetol hydroge-
nates to 1,2-PDO over the metal particles (Alhanash et al., 2008;
Chaminand et al., 2004; Dasari et al., 2005; Furikado et al., 2007;
Miyazawa et al., 2006a,b, 2007; Wang and Liu, 2007). On the other
hand, this reaction proceeds consecutively in three steps in alkali
solution. That is, glycerol rstly dehydrogenates to glyceraldehy-
des, followed with glyceraldehydes dehydrates to 2-hydroxyacro-
lein and 2-hydroxyacrolein hydrogenates to 1,2-PDO (Feng et al.,
2007, 2008; Maris et al., 2007; Maris and Davis, 2007; Montassiera
et al., 1991). These suggestions are summarized and illustrated in
Scheme 1.
According to the reaction mechanism, hybrid Ru/C (or
Rh/SiO
2
) + solid acids catalysts (Furikado et al., 2007; Miyazawa
et al., 2006a,b, 2007) and a ruthenium-doped acidic heteropoly
salt Cs
2.5
H
0.5
[PW
12
O
40
] (Alhanash et al., 2008) were reported for
hydrogenolysis of glycerol. In these conditions, 1,2-PDO formed
via a dehydration and hydrogenation routine (in Scheme 1).
At the same time, Pt/C and/or Ru/C catalyst plus alkali (NaOH or
Ca(OH)
2
) were also reported by Maris and Davis according to the
alkali-catalyzed mechanism (Maris and Davis, 2007; Maris et al.,
2007). They found that the addition of alkali enhanced the reactiv-
ity of Pt to a greater extent than that of Ru and the main product
was 1,2-PDO. But the added alkali such as NaOH promoted the
cleavage of CC bonds and the formation of lactate.
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.04.016
* Corresponding author. Tel.: +86 571 88273272; fax: +86 571 88273283.
** Corresponding author. Tel.: +86 571 88273272; fax: +86 571 88273283.
E-mail address: zyhou@zju.edu.cn (Z. Hou).
Bioresource Technology 101 (2010) 70887092
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
Besides the hybrid Ru/C (or Rh/SiO
2
) + Amberlyst, Pt/C(or Ru/
C) + NaOH catalyst, single Raney Ni, Pt/C, Pd/C, Ru/C and Ni/C were
also reported for the hydrogenolysis of glycerol to 1,2-PDO. But the
reported activity and selectivity of 1,2-PDO was low even under
severe reaction conditions (Chaminand et al., 2004; Perosa and
Tundo, 2005).
According to the reaction mechanism of hydrogenolysis of glyc-
erol to 1,2-PDO proposed above (1), we can deduce that a solid
bifunctional catalyst consisting of metal and acidic (or basic) sites
would be an alternate instead of the hybrid catalysts. In our previ-
ous work, hydrotalcite, MgO, Al
2
O
3
, H-ZSM5 and H-Beta supported
Pt catalysts were prepared and tested for hydrogenolysis of glyc-
erol to 1,2-PDO (Yuan et al., 2009). It was found that solid base
(hydrotalcite and MgO) supported Pt catalysts exhibited the pre-
dominant activity and higher 1,2-PDO selectivity than that of solid
acids (Al
2
O
3
, H-ZSM5 and H-Beta). Characterization results re-
vealed that the alkaline strength of the catalyst contributed obvi-
ously to its activity for glycerol hydrogenolysis. At the same
time, solid base supported catalysts also possess advantages in
environmental friendly, easiness in separation and recycle. And
the cleavage of CC bonds in Pt/C + NaOH system was repressed
efciently.
In present work, we want to report a solid MgO supported non-
noble metal (CuO/MgO) catalyst, which is highly efcient for
hydrogenolysis of glycerol to 1,2-PDO in a moderate conditions.
The catalyst preparation methods such as impregnation and copre-
cipitation were disclosed in detail. Those highly active catalysts
were characterized by X-ray diffraction (XRD), transmission elec-
tron microscopy (TEM), N
2
-adsorption and temperature-pro-
grammed reduction with H
2
(H
2
-TPR). The relation between the
performance for hydrogenolysis of glycerol to 1,2-PDO and the
structure of CuO/MgO were discussed.
2. Methods
2.1. Catalyst preparation
Firstly, calculated amount of CuCl
2
2H
2
O (Shanghai Chemicals,
China, AR) and MgCl
2
6H
2
O (Shanghai Chemicals, China, AR) were
dissolved in distilled water under stirring, and the solution was re-
ferred as A. Solution B was aqueous Na
2
CO
3
with a concentration of
1.0 mol/L. Secondly, solution B was added to solution A at a rate of
one drip per second under vigorously stirring at room temperature
until the pH of the mixed solution reached 10.5. After that, the pre-
cipitate was aged at room temperature for 12 h followed by ltra-
tion and thoroughly washed with deionized water until the
ltrates were free of chloride. This precipitate was dried in ambient
air at 110 C overnight and calcined at 550 C for 4 h. Three cata-
lysts with copper loading amount of 10, 15 and 20 wt.% were pre-
pared in above procedures, which were identied as Cu-x/MgO-CP;
x referred the loading amount of copper.
CuO/MgO catalysts were also prepared via impregnation and
used as reference samples. MgO (Shanghai Chemicals, China, AR)
was rstly pretreated at 550 C for 4 h, and impregnated in an
aqueous solution of Cu(NO
3
)
2
3H
2
O (Shanghai Chemicals, China,
AR) for 4 h. And then the precursor was dried in ambient air at
110 C overnight followed by calcination at 550 C for 4 h. Catalysts
prepared in this procedure were identied as Cu-x/MgO-IM, in
which x referred the loading amount of copper.
2.2. Catalytic reaction
All fresh CuO/MgO catalysts were rstly reduced in H
2
at 350 C
for 1 h before they were used for hydrogenolysis of glycerol. The
hydrogenolysis of glycerol was carried out in a custom-designed
50 mL stainless steel autoclave equipped with inner Teon coating
and a thermoelectric couple. Aqueous solution of glycerol (75 wt.%,
8.0 ml) and 1.0 g reduced Cu/MgO catalyst were rstly added to the
reactor. The autoclave was purged with H
2
for 5 times and pres-
sured to 3.0 MPa, put in an oil bath preheated to the required tem-
perature and maintained at that temperature for a given period
under vigorously stirring with a magnetic stirrer (MAG-NEO, RV-
06 M, Japan). After reaction, the reactor was cooled to room tem-
perature; vapor phase was collected by a gas-bag and analyzed
using a gas chromatograph (Shimadzu, 8A) equipped with an
active carbon column and a thermal conductivity detector (TCD).
Liquid phase was centrifuged to remove the solid catalyst powder
and analyzed using a gas chromatograph (Shimadzu, 14 B)
equipped with a 30 m capillary column (DB-WAX 52 CB, USA)
and a ame ionization detector (FID).
2.3. Catalyst characterization
The actual loading amount of copper in prepared catalysts was
checked and conrmed by inductively coupled plasma-atomic
emission spectroscopy (ICP, Plasma-Spec-II spectrometer).
Surface areas of the prepared CuO/MgO catalysts were mea-
sured by N
2
physisorption at its normal boiling point (196 C)
using an ASAP 2010 analyzer (Micromeritics). The catalysts were
rstly degassed at 250 C for 4 h (<2.66 Pa) before adsorption.
XRD spectra of the prepared CuO/MgO catalysts were obtained
in a 2h range of 1080 on a Rigaku D/MAX-2500 diffractometer
using Cu Ka radiation (k = 1.5406 ). The crystallite size (D) of
MgO was calculated by Scherrer equation, D = 0.90k/bcosh, where
h is the diffraction angle and b is the full width at half-maximum
(FWHM).
TEM images of the reduced Cu/MgO catalysts were recorded
using an accelerating voltage of 200 kV (JEOL-2010F). Catalysts
were rstly ground to powder, reduced in hydrogen at 350 C for
1 h, and dispersed on Au grids in tetrachloromethane under super-
sonic-wave shaking. The fast Fourier transforms (FFT) was em-
ployed to identify Cu and MgO particles.
OH
OH O H
-H
2
O
O
O H
+H
2
OH
O H
Glycerol
1,2-propanediol Acetol
-H
2
O
OH
OH
-H
2
O
O
OH
+H
2
Glyceraldehyde
2-Hydroxyacrolein
OH
O H
1,2-propanediol
a
c
i
d

c
a
t
a
l
y
s
t
a
l
k
a
l
i
Scheme 1. Hydrogenolysis of glycerol to 1,2-PDO.
Z. Yuan et al. / Bioresource Technology 101 (2010) 70887092 7089
H
2
-TPR of CuO/MgO catalysts was performed in a quartz reac-
tor. Catalysts were rstly loaded and pretreated at 550 C for 1 h
under N
2
ow (30 ml/min). After cooled to room temperature,
the reduction agent (10% H
2
/N
2
mixture, 30 ml/min) was switched
and the reactor was heated to 550 C at a rate of 10 C/min. Efuent
gas was dried by powder KOH and hydrogen consumption was
analyzed by a thermal conductivity detector (TCD). The amounts
of hydrogen consumption were calibrated using known amounts
of CuO.
3. Results and discussion
3.1. Hydrogenolysis of glycerol
Table 1 summarized the activities of glycerol hydrogenolysis
over reduced Cu/MgO catalysts at 180 C. It can be found that
hydrogenolysis of glycerol to 1,2-PDO performed successfully on
Cu/MgO catalysts prepared via coprecipitation. Cu-10/MgO-CP
had a 48.6% conversion of glycerol and a 97.4% selectivity of 1,2-
PDO. When the loading amount of copper increased to 15 wt.%,
the conversion of glycerol reached to 72.0% and the selectivity of
1,2-PDO remained at 97.6%. This performance is higher than that
of solid acids supported copper catalysts (Guo et al., 2009) and is
comparable with that of hybrid Ru/C(or Rh/SiO
2
) + Amberlyst and
Pt/C(or Ru/C) + NaOH. However, the conversion of glycerol dropped
to 58.4% when the copper loading further increased to 20 wt.%.
These results could be attributed to that when copper loading in-
creased from 10 to 15 wt.%, the number of available active copper
sites for hydrogenation increased. But the reuniting of active cop-
per sites might happen when the loading amount further increased
to 20 wt.%.
Small amount of NaOH further increased the activity of Cu-15/
MgO-CP for glycerol hydrogenolysis and the detected conversion of
glycerol increased to 82.0% with a 95.8% selectivity of 1,2-PDO.
According to the reaction kinetics of the hydrogenolysis of lower
polyhydric alcohols proposed by Lahr and Shanks (Lahr and
Shanks, 2003), glycol adsorbs on the catalyst and reacts to form
an aldehyde or ketone rstly. The formed aldehyde or ketone spe-
cies desorbs and is subsequently degraded by hydroxyl attack in
the basic solution, CC and CO cleavage steps in the degradation
of higher polyols to lower polyols are catalyzed by bases; thus, the
pH of the system accelerates the overall rate. This promotion effect
of NaOH for hydrogenolysis of glycerol was also recommended by
Maris and Davis (Maris and Davis, 2007).
Cu-10/MgO-IM showed the lowest activity for hydrogenolysis
of glycerol to 1,2-PDO among all the tested Cu/MgO catalysts, with
a 22.0% conversion of glycerol and a 86.7% selectivity of 1,2-PDO.
This might be attributed to that the dispersion of Cu in Cu/MgO
catalysts prepared via impregnation is lower than that prepared
via coprecipitation. The conversion of glycerol increased slightly
from 22.0% to 30.0% when the copper loading amount increased
from 10 to 15 wt.%. On the other hand, the conversion of glycerol
dropped to 25.6% when the loading amount of copper further in-
creased to 20 wt.%. This phenomenon could be also attributed to
that the sintering of active copper sites occurred when the loading
amount is higher because the surface area of support MgO is lim-
ited (34.0 m
2
/g, Table 2).
Time course of glycerol hydrogenolysis to 1,2-PDO over Cu-15/
MgO-CP catalyst is shown in Fig. 1. It can be found that the conver-
sion of glycerol increased quickly from 29.1% (at 5 h) to 90.1% in
the rst 30 h, after that it increased slightly to 94.2% with the pro-
longed time to 40 h. During the time course, the selectivity of 1,2-
PDO only decreased slightly from 98.0% to 96.4%. These results
indicated that the conversion of glycerol is depended on its con-
centration in the reaction mixture, while the higher selectivity of
1,2-PDO inferred that solid base supported catalyst is efcient to
depress the cleavage of CC bond even at a longer reaction time.
3.2. Chemical and physical properties of the catalysts
Table 2 summarized the BET surface area of the prepared cata-
lysts detected by N
2
adsorption. When the copper loading amount
increased from 10 to 20 wt.%, the surface areas of CuO/MgO cata-
lysts prepared by coprecipitation decreased sharply from 26.2 to
11.9 m
2
/g, and this is attributed to that the surface of MgO was
occupied by bigger sized CuO particles. This signicant decrease
in surface area should lead to the decrease in catalytic activity
(Table 1).
Table 1
Glycerol hydrogenolysis over Cu/MgO catalysts.
a
Catalyst Glycerol conversion (%) Selectivity (%)
1,2-PDO 1,3-PDO EG
CuO-10/MgO-CP 48.6 97.4 0.8
CuO-15/MgO-CP 72.0 97.6 1.3
CuO-20/MgO-CP 58.4 96.8 0.8
CuO-15/MgO-CP
b
82.0 95.8 0.3
CuO-10/MgO-IM 22.0 86.7 8.5
CuO-15/MgO-IM 30.0 92.8 3.0
CuO-20/MgO-IM 25.6 93.2 2.8
a
Reaction conditions: 75 wt.% aqueous solution of glycerol 8.0 ml, 1.0 g of
reduced catalyst, H
2
pressure 3.0 MPa, 180 C, 20 h.
b
0.125 g NaOH was added.
Table 2
Chemical properties of the Cu/MgO catalysts.
Catalyst MgO crystallite
size
b
(nm)
Cu particle
size
c
(nm)
S
BET
(m
2
/g)
CuO-10/MgO-CP 24.3 3.2 26.2
CuO-15/MgO-CP 22.9 4.0 25.6
CuO-20/MgO-CP 22.6 23.0 11.9
CuO-10/MgO-IM 36.7 10.7 ND
d
MgO
a
34.0
a
Magnesia from Shanghai Chemicals, AR.
b
Detected by XRD characterization.
c
Calculated in TEM analysis.
d
Not detected.
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30 35 40 45
Reaction time (h)
C
o
n
v
e
r
s
i
o
n

&

S
e
l
e
c
t
i
v
i
t
y

(
m
o
l
%
)
Conversion
Selectivity
Fig. 1. Time course of glycerol hydrogenolysis to 1,2-PDO over Cu-15/MgO-CP.
7090 Z. Yuan et al. / Bioresource Technology 101 (2010) 70887092
XRD analysis found that both Cu-10/MgO-CP and Cu-10/MgO-
IM catalysts have characteristic diffraction peaks of MgO (face-cen-
tered cubic) and the calculated crystallite sizes of MgO are 24.3 nm
(in Cu-10/MgO-CP) and 36.7 nm (in Cu-10/MgO-IM), respectively.
The diffraction peaks of CuO appeared only in the XRD patterns
of CuO/MgO prepared by impregnation (see Fig. S-1 in Supplemen-
tary material). These results indicated that a well dispersed copper
oxide particles formed on the surface of MgO in the catalyst pre-
pared via coprecipitation.
At the same time, XRD analysis also disclosed that the diffrac-
tion peaks of CuO appeared in Cu-15/MgO-CP and became sharper
Cu-20/MgO-CP (see Fig. S-2 in Supplementary material). These re-
sults suggested that the dispersion of CuO on MgO became lower
and bigger CuO particles formed. As the conversion of glycerol
decreased from 72.0% (on Cu-15/MgO-CP) to 58.4% (on Cu-20/
MgO-CP) under the same reaction condition, we think that smaller
copper particles are more active for glycerol hydrogenolysis. The
calculated crystallite sizes of MgO in these catalysts are 24.3,
22.9 and 22.6 respectively.
The particle sizes of Cu and MgO in these catalysts were also de-
tected by TEM analysis. It was found that Cu/MgO catalysts pre-
pared by coprecipitation appeared the cross-linked rod outline
with a diameter sized in 10 to 35 nm, while a lot of separated par-
ticles sized in 3075 nmappeared in the TEMimage of Cu/MgOpre-
pared by impregnation (see Fig. S-3 in Supplementary material).
The calculated copper particle sizes in Cu-15/MgO-CP, Cu-20/
MgO-CP and Cu-10/MgO-IM in their TEM images are 4.0, 23.0 and
10.7 nm, respectively (summarized in Table 2). The foregoing glyc-
erol hydrogenolysis experiments (in Section 3.1) disclosed that the
conversions of glycerol on these catalysts are 72.0, 58.4 and 22.0%.
These data further conrmed that smaller copper particle is more
active for this reaction. At the same time, the lower activity of
Cu-10/MgO-IM than that of Cu-20/MgO-CP could be attributed to
that the particle size of MgO also possesses signicant impact on
its performance.
H
2
-TPR analysis found that all of Cu-10/MgO-CP, Cu-15/MgO-
CP, Cu-10/MgO-IM and Cu-15/MgO-IM catalysts contain highly
dispersed CuO particles with a weak interaction with MgO support
(Anderson et al., 1997; Carniti et al., 2000; Suh et al., 2000), highly
dispersed CuO particles that have a strong interaction with the
support and big sized CuO particles dispersed on the surface of
MgO (see Fig. S-4 in Supplementary material). H
2
-TPR analysis also
found highly dispersed Cu species (reduced from the rst two
peaks) improved the reduction of the big sized CuO species, be-
cause the reduction temperature of the third peak shifted from
363 C (in Cu-10/MgO-IM) to 335 C (in Cu-15/MgO-IM). These dif-
ferent copper species are consistent with their unevenly dispersion
detected in TEM analysis.
4. Conclusion
It was found that bifunctional solid Cu/MgO catalysts are ef-
cient for hydrogenolysis of glycerol to 1,2-PDO instead of the hy-
brid Ru/C(or Rh/SiO
2
) + Amberlyst and Pt/C(or Ru/C) + NaOH. Cu/
MgO catalyst prepared via coprecipitation has the cross-linked
rod outline, smaller copper particles and higher activity. Small
amount of NaOH can further increase the conversion of glycerol.
Characterization results indicated that smaller sized Cu and MgO
particles are more active for glycerol hydrogenolysis.
Acknowledgements
This research work was supported by Zhejiang Provincial Natu-
ral Science Foundation (Grant No. Z406142), the National Natural
Science Foundation of China (Contract No. 90610002) and the Min-
istry of Science and Technology of China through the National Key
Project of Fundamental Research (Contract No. 2007CB210207).
Appendix A. Supplementary data
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.biortech.2010.04.016.
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