Hydrogenolysis of glycerol over Pt/C catalyst in combination with alkali metal hydroxides

Article abstract of DOI:10.1515/chem-2016-0030

The hydrogenolysis of glycerol was performed over a Pt/C catalyst in combination with several alkali metal hydroxides and their salts. LiOH was found to be an effective promoter for the selective hydrogenolysis of glycerol to 1,2-propanediol. Hydroxyl ions are the main factor to promote the reaction process by dehydration of the glyceraldehyde intermediate. Lithium ions play a role in assisting the dehydrogenation of glycerol to glyceraldehyde, because they have the right size to coordinate with the alkoxide species. A possible surface reaction mechanism involving the participation of lithium ions was proposed to account for the results obtained in the study.

Full text of DOI:10.1515/chem-2016-0030

Open Chem., 2016; 14: 279–286
Short Communication
Open Access
Jian Feng*, Wei Xiong, Hao Ding, Bai He
Hydrogenolysis of glycerol over Pt/C catalyst
in combination with alkali metal hydroxides
DOI 10.1515/chem-2016-0030
received October 17, 2016; accepted November 22, 2016.
catalytic hydrogenolysis to 1,2-propanediol (1,2-PDO) and
1
,3-propanediol[3-5].Bothofthediolproductsareimportant
Abstract: The hydrogenolysis of glycerol was performed chemicals for the production of polyesters, resins and
over a Pt/C catalyst in combination with several alkali metal polyurethanes, but the current production methods of the
hydroxidesandtheirsalts. LiOHwasfoundtobeaneffective two propanediols are based on petrochemical feedstocks.
promoter for the selective hydrogenolysis of glycerol to Therefore, the hydrogenolysis of biomass-derived glycerol
1
,2-propanediol. Hydroxyl ions are the main factor to to propanediols is a promising green method. Considering
promote the reaction process by dehydration of the the possibility of industrialization in the near future, the
glyceraldehyde intermediate. Lithium ions play a role in hydrogenolysis of glycerol to 1,2-PDO has much potential
assistingthedehydrogenationofglyceroltoglyceraldehyde, and practical use [6].
because they have the right size to coordinate with the
The hydrogenolysis of glycerol has been investigated
alkoxide species. A possible surface reaction mechanism over various heterogeneous catalysts [3-5]. Among the
involving the participation of lithium ions was proposed to catalysts studied, Pt-based catalysts have been found to be
account for the results obtained in the study.
relatively efficient for the production of propanediols due
to their high selectivity for the cleavage of C–O bond [5,7].
To further improve the catalytic performance, Pt catalysts
are usually used in the presence of some additives [7, 8 ].
For example, tungsten containing compounds such as
WO , H WO , and H SiW O were reported as effective
Keywords: Glycerol, hydrogenolysis, platinum,
1,2-propanediol, lithium cation
3
2
4
4
12 40
1
Introduction
additives for the promotion of 1,3-propanediol selectivity
over Pt-based catalysts [8-12]. Furthermore, the addition
The production of commodity chemicals from biomass- of a certain base like NaOH or CaO to the Pt catalytic
derived molecules is a promising and sustainable system was found to be an efficient method to increase
alternative to the current industrial practice. In particular, the reactivity and 1,2-PDO selectivity [13-16]. Maris et al.
glycerol has been identified by the U.S. Department of [13,14] reported that the addition of NaOH enhanced the
Energy as one of the top-12 platform molecules that can reactivity of Pt to a greater extent. In fact, not only the
be obtained from biomass [1]. Traditionally, glycerol is catalytic performance of Pt, but also that of Cu [1 7,1 8 ], Ru
producedasabyproductintheprocessofsoapmanufacture [19-22], and Ni [18] can be improved by basic additives in
or fatty acid production. In recent years, owing to the the glycerol hydrogenolysis reaction. In our previous works
rapid development of the biodiesel industry, large [19-21], we have revealed that alkali metal hydroxides
amounts of glycerol are available as a low-cost byproduct. are suitable additives for the hydrogenolysis of glycerol
As a consequence, the conversion of glycerol to other high to 1,2-PDO over Ru catalysts. As shown in Scheme 1,
value-added products has drawn widespread attention [2]. under basic conditions, the hydrogenolysis reaction
One attractive route for the utilization of glycerol involves firstly occurs via a reversible dehydrogenation of glycerol
to glyceraldehyde on the metal sites (step 1). Then,
glyceraldehyde undergoes base-catalyzed dehydration to
2
-hydroxyacrolein (step 2), which is finally hydrogenated
*
Corresponding author: Jian Feng: College of Chemistry and
–
to 1,2-PDO (step 3). The hydroxyl ion (OH ) can promote
Chemical Engineering, Chongqing University of Science & Technology,
Chongqing 401331, China, E-mail: fengjianscu@163.com
Wei Xiong, Hao Ding, Bai He: College of Chemistry and Chemical
Engineering, Chongqing University of Science & Technology,
Chongqing 401331, China
the dehydration of glyceraldehyde, thereby increasing
the glycerol conversion and 1,2-PDO selectivity. This
inspired us to develop a catalytic system for Pt catalysts in
combination with basic promoters.
©
2016 Jian Feng et al., published by De Gruyter Open.
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280ꢀ
ꢀ Jian Feng et al.
OH
OH
OH
OH
-
H2
- H O
+ H2
2
O
OH
O
HO
OH
OH
OH-
metal
metal
Glycerol
Glyceraldehyde
2-Hydroxyacrolein
1
,2-PDO
step 1
step 3
step 2
Scheme 1: Hydrogenolysis of glycerol to 1,2-PDO under basic conditions.
Although the importance of basic promoters to the obtained by JEM-1200EX at 100 kV. Scanning transmission
catalytic performance of Pt has been demonstrated in electron microscopy (STEM), high-resolution transmission
some works, little research has focused on the effect of the electron microscopy (HRTEM), and energy dispersive
base type, and very limited details are known about the X-ray (EDX) measurements were recorded on a JEOL-2100F
role of the metal cation in the reaction process. Therefore, electron microscope operated at 200 kV. The sample was
in this study, the hydrogenolysis of glycerol was performed ultrasonically suspended in ethanol and deposited on
over a Pt/C catalyst in combination with several inorganic a Cu grid recovered with a thin layer of carbon.
bases, with the aim of selecting a good basic promoter for
Hydrogenolysis of glycerol was performed in a 20 mL
the Pt catalytic system. The role of the alkali metal cation stainless steel autoclave equipped with a magnetic stirrer
–
and OH in the reaction process was discussed with a and an electric temperature controller. The Pt/C catalyst
proposed surface reaction mechanism.
was pre-reduced in the same autoclave. The catalyst, alkali
metal hydroxides or salts, and glycerol aqueous solution
were charged into the autoclave in desired amounts.
The reactor was sealed and purged repeatedly with
hydrogen to eliminate air, pressurized to the necessary
2
Experimental Procedure
The active carbon-supported Pt catalyst with a metal hydrogen pressure, and then heated to the desired
loading of 5 wt% was obtained from the Institute temperature. The detailed reaction conditions are
of Homogenous Catalysis, Sichuan University. The described in Table 1. Af er the reaction, the products in the
catalyst was prepared by an impregnation technique. liquid phase were analyzed by GC (Agilent 6890N, Agilent
Weighed amounts of the active carbon were impregnated Technologies) equipped with a flame ionization detector
with the aqueous solution of chloroplatinic acid and a capillary column (Supelco WAXTM, 30 m × 0.53 mm
hexahydrate (Aladdin). The slurry was stirred × 1 µm). The gas products were qualitatively checked by
overnight at room temperature. Then, the solvent was GC (9790, Shanghai HaiXin) equipped with a molecular
removed under reduced pressure. Subsequently, the sieve packed column and a thermal conductivity detector.
resulting powder was reduced in an autoclave with
The conversion of glycerol and the selectivity in liquid
a hydrogen atmosphere (3 MPa) in ethylene glycol at products were calculated on a carbon basis according to
o
2
00 C. The reduced catalysts were washed repeatedly the following equations:
with deionized water and acetone, and then dried at
–
–
–
Conversion of glycerol (%) = (moles of glycerol con-
sumed/moles of glycerol initially charged) × 100.
Selectivity (%) = (moles of carbon in specific product/
moles of carbon in all detected products) × 100.
For details, refer to the method described in previous
works [23,24].
o
6
0 C in vacuum for 4 h prior to the reaction. Glycerol,
alkali metal hydroxides and their salts, and other reagents
were commercially obtained as AR samples and used as
received.
The BET surface area of Pt/C was measured on an
auto adsorption/desorption analyzer (ZXF-6, Northwest
Chemical Industry) using nitrogen as the adsorbate.
Powder X-ray diffraction (XRD) measurements were 3 Results and Discussion
performed on an X’Pert Pro MPD diffractometer (Philips)
equipped with a Cu Kα radiation source (40 kV, 25 mA, The BET surface area of the Pt/C catalyst was determined
2
λ = 0.15406 nm). About 50 mg of catalyst samples were to be 341 m /g. The XRD pattern of Pt/C is given in Figure 1.
pressed in the sample holder. The XRD patterns were The major phase presented in the diffractogram is
obtained with a scan rate of 2s/step and a step size of 0.05o amorphous carbon, with a broad diffraction peak at
o
o
(
2θ). Transmission electron microscopy (TEM) images were 2θ = 24.5 [16]. The sharp peak at 2θ = 26.4 indicates that
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Hydrogenolysis of glycerol over Pt/C catalyst in combination with alkali metal hydroxidesꢀ
ꢀ281
Table 1: Catalytic performance of Pt/C in the presence of alkali metal hydroxides and salts.a
Entry
Base or salt
Conversion (%)
Selectivity (%)b
,2-PDO
1
EG
PO
5.5
3.6
3.8
4.3
–
EO
1.5
0.9
1.2
1.8
–
MO
0.8
0.4
0.3
1.0
–
1
–
11.5
42.8
36.4
33.4
<1.0
53.9
18.5
7.8
78.8
90.2
87.7
86.9
Trace
57.7
12.3
4.2
5.5
5.3
–
2
3
4
5
6
7
8
9
LiOH
NaOH
KOH
LiOHc
LiOHd
Li CO
3.8
5.1
9.4
3.9
7.1
3.2
8.9
5.0
2.5
1.3
0.7
1.2
1.4
1.6
0.4
0.9
88.2
77.1
2
3
LiCl
KOH + LiOHe
42.3
87.1
a
b
c
o
Reaction conditions: 180 C, 3 MPa, 12 h, 5 mL 20 wt% glycerol aqueous solution, 195 mg Pt/C, 1mmol base or salt.
,2-PDO: 1,2-Propanediol; EG: ethylene glycol; PO: 1-propanol and 2-propanol; EO: ethanol; MO: methanol.
1
Without Pt/C.
d
e
3
0
mmol LiOH.
.5mmol KOH and 0.5mmol LiOH.
a small amount of graphite (JCPDS Card #41-1487) coexists
in the active carbon support. This probably accounts for
the relatively low surface area of the Pt/C catalyst. No
obvious diffraction peaks can be assigned to Pt crystalline
phase (2θ = 39.8 , 46.2 and 67.5 ; JCPDS Card #04-0802),
suggesting that Pt is well dispersed as small particles on
the active carbon.
G ra p h ite
o
o
o
A representative TEM image of the Pt/C catalyst is
shown in Figure 2. As it can be seen in the micrograph,
the dispersion of Pt nanoparticles is fairly good, which is
in accordance with the XRD result. The average particle
size of Pt is around 4.5 nm. The bright field STEM image of
the Pt/C catalyst is shown in Figure 3a. To further confirm
that those dark spots in the STEM are Pt nanoparticles, we
used EDX analysis to measure the elemental distribution
of a selected area with (area 1 in Figure 3a) and without
1
0
2 0
3 0
4 0
5 0
6 0
7 0
2
T h e ta / d e g re e
(
area 2 in Figure 3a) a dark spot. The EDX spectrum of
area 1 (Figure 3b) shows obvious Pt signals at 2.1 keV,
.4 keV and 11.2 keV, whereas no obvious Pt signal can
Figure 1: XRD pattern of the Pt/Ccatalyst.
9
be observed in area 2 (Figure 3c). This indicates that the catalytic performance of Pt/C. Alkali metal hydroxides
dark spots in the STEM are mainly Pt nanoparticles. The were used as promoters because they are inexpensive
unmarked peaks in the EDX spectra are attributed to the and easily available. As presented in Table 1 (Entries 1 to
background Cu signals resulting from the grid used to 4), the addition of alkali metal hydroxides significantly
hold the sample. Figure 4 shows a HRTEM image of the Pt increased the conversion of glycerol and the selectivity to
nanoparticles and the corresponding intensity profile. As 1,2-PDO. The highest conversion of glycerol and the highest
presented in Figure 4a, the Pt nanoparticles exhibit good selectivity to 1,2-PDO were obtained in the presence of
crystallinity. According to the intensity profile in Figure LiOH. As far as the production of 1,2-PDO is concerned,
4
b, the interplanar distance is 0.19 nm, corresponding to Pt/C is far superior to Ru catalysts under similar reaction
the (200) planes of platinum. conditions [20]. Moreover, the selectivity to ethylene
According to the reaction pathway shown in Scheme glycol (a main undesired degradation product) decreased
, we envisaged using some basic additives to improve the no matter which basic additive was added. This is because
1
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282ꢀ
ꢀ Jian Feng et al.
4 0
M e a n s iz e : 4 .5 n m
3 0
2 0
1 0
0
1
2
3
4
5
6
7
8
9
P t p a rtic le s iz e (n m )
Figure 2: TEM image and particle size distribution of the Pt/C catalyst.
Figure 3: (a) Bright field STEM image of the Pt/C catalyst; (b) Corresponding EDX elemental analysis from area 1 (red circle) in the STEM
image; (c) Corresponding EDX elemental analysis from area 2 (blue circle) in the STEM image.
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Hydrogenolysis of glycerol over Pt/C catalyst in combination with alkali metal hydroxidesꢀ
ꢀ283
of the secondary hydroxyl group in the glyceraldehyde
molecule is very difficult under basic conditions [19]. In
order to avoid the formation of undesired side products,
optimized reaction conditions were used, as given in Table
1
. Using LiOH as a basic promoter for Pt/C, the 1,2-PDO
selectivity can be comparable to Cu catalysts [4], whereas
the reaction conditions are much milder.
Comparison of Entries 2, 3 and 4 in Table 1 shows
that different basic promoters have different effects on the
catalytic activity. The alkali metal hydroxides influenced
the Pt/C activity in the order of LiOH > NaOH > KOH.
Because all of the three bases are strong bases and can
fully dissociate in the water solvent, this behavior is not
–
attributed to the concentration of OH . A previous study
has reported that the metal cation may have a role in the
complexation of the hydroxyl group in the reaction of
glycerose with alkali [27]. Therefore, the different effect on
the catalytic activity is more likely to be associated with
the size of the metal cation.
On the basis of the above experimental results and
+
discussions, webelievethatlithiumions(Li )havetheright
size to take part in the glycerol hydrogenolysis reaction in
basic aqueous solution. The verifying experiments were
carried out in which some lithium salts or mixed alkali
metal hydroxides were added to the catalytic system.
As listed in Entry 7 of Table 1, Li CO can also promote the
Figure 4: (a) HRTEM image of Pt nanoparticles; (b) Intensity profile
created by Digital Micrograph on the marked Pt nanoparticle in the
HRTEM image.
2
3
–
OH in the aqueous solution can suppress the scission of hydrogenolysis of glycerol to 1,2-PDO in high selectivity,
C–C bonds [5,25]. A blank reaction was performed with but the reaction activity only slightly increased. This
LiOH in the absence of a Pt/C catalyst (Entry 5, Table 1); result may not be very informative since the solubility
however, almost no reaction occurred. Similar phenomena of Li CO in water is low. It may not completely dissolve
2
3
was observed in the blank reactions of NaOH and KOH, in the aqueous solution. More valuable information
indicating that basic additives are unable to catalyze the can be obtained from the addition of LiOH mixed with
–
hydrogenolysis of glycerol independently, and the metal KOH (Entry 9, Table 1). The concentration of OH in this
catalyst is necessary for the reaction. In fact, the metal mixed system is the same as that of the neat KOH system
sites serve both as dehydrogenating and hydrogenating (Entry 4, Table 1), but the catalytic activity was much
functions in the overall reaction process (step 1 and step higher, and can even be comparable to that of the neat
3
in Scheme 1).
LiOH system (Entry 2, Table 1). When LiCl was added
It should be pointed out that the dosage of alkali (Entry 8, Table 1), the reaction occurred more slowly, which
metal hydroxides can influence the product selectivity. maybe due to the poisonous effect of the chloride ion. This
–
+
We have studied the effect of the amount of base on the experiment also suggests that, without enough OH , Li
catalytic performance of Ru/TiO , and have found that an cannot obviously promote the glycerol hydrogenolysis
2
excess of LiOH will reduce the formation of 1,2-PDO [19]. In reaction (Entries 7 and 8, Table 1).
this work, experiments with an excess of LiOH, NaOH or
Taken together, we can reasonably conclude that:
–
KOH were also tested for promotion of the Pt/C catalyst 2. (1) OH is the main factor to promote the dehydration
The selectivity of 1,2-PDO significantly decreased when of glyceraldehyde; (2) Li+ can aid the hydrogenolysis
–
the amount of the base exceeded 3 mmol (Entry 6, Table reaction, but it needs the presence of adequate OH . These
1
). The work of Maris et al. [13] shows that lactic acid is conclusions can be explained as follows according to the
formed at higher pH. Actually, lactic acid can be produced reaction mechanism shown in Scheme 2.
by a Cannizzaro reaction from the 2-hydroxyacrolein
Although some previous studies have proposed
intermediate [22,26]. In addition, there is scarcely any 1,3- reaction pathways for the hydrogenolysis of glycerol to
propanediolintheliquidproducts,becausetheelimination 1,2-PDO, few works have concerned the possible surface
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284ꢀ
ꢀ Jian Feng et al.
OH
a
OH
+
HO
OH
H2
Li ,
OH
Pt
e
Li
OH
H
HO
HO
O
O
H
H
(
ad)
H
H
H
H
H
Pt
H
H
Pt
b
Li
d
-
Li
OH
OH
H
HO
HO
OH
+
Li + H O
2
H
H
H
O
O
H
c
(ad)
H
H
H
H
Pt
H
H
Pt
Scheme 2: A possible mechanism for hydrogenolysis of glycerol to 1,2-PDO over Pt/C in the presence of LiOH. Steps a-c: dehydrogenation of
glycerol to glyceraldehyde; step d: dehydration of glyceraldehyde to 2-hydroxyacrolein; step e: hydrogenation of 2-hydroxyacrolein to 1,2-PDO.
+
reactions. The mechanism illustrated in Scheme 1 cannot Scheme 2). Water and free Li are also formed in this step.
show the detailed heterogeneous reaction process. Based Finally, hydrogenation of 2-hydroxyacrolein gives 1,2-PDO
on the results and discussions above, it is proposed (step e in Scheme 2). It is worth mentioning that the step d
+
that Li is involved in the dehydrogenation of glycerol must be much faster than the dehydrogenation of glycerol,
to glyceraldehyde (steps a–c in Scheme 2). Initially, so that the reversible dehydrogenation-hydrogenation
the dissociative adsorption of glycerol on the surface equilibrium between glycerol and glyceraldehyde can
of Pt nanocluster forms alkoxide and hydride species. proceed forward [3-5]. Otherwise, glyceraldehyde will
+
Simultaneously, Li interacts with the two hydroxyl groups be hydrogenated back to glycerol over the metal sites. In
of alkoxide, thereby stabilizing the reactive alkoxide addition, although the hydride species can be generated
species. Hydrogen is also dissociated and adsorbed on the from the glycerol (H in blue in Scheme 2), external
Pt surface. Then, the α-H of an alkoxide undergoes hydride hydrogen gas is necessary to ensure that the hydrogenation
abstraction to yield a hydride species and adsorbed of 2-hydroxyacrolein works smoothly.
–
glyceraldehyde on Pt. Successively, OH attacks the
Our proposed reaction mechanism can reasonably
hydrogen at the middle carbon atom of glyceraldehyde, explain the results in this study, and it may give some
which makes the primary hydroxyl group readily removed valuable insights for further investigation. However,
by dehydration to form 2-hydroxyacrolein (step d in we should point out that the mechanism depicted in
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Hydrogenolysis of glycerol over Pt/C catalyst in combination with alkali metal hydroxidesꢀ
ꢀ285
Scheme 2 is not very specific. Although the coordination [8] Dam J., Djanashvili K., Kapteijn F., Hanefeld U., Pt/Al O3
2
+
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2
3
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[
–
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+
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Unauthenticated
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