Propylene from renewable resources: Catalytic conversion of glycerol into propylene

Article abstract of DOI:10.1002/cssc.201301041

Propylene, one of the most demanded commodity chemicals, is obtained overwhelmingly from fossil resources. In view of the diminishing fossil resources and the ongoing climate change, the identification of new efficient and alternative routes for the large-scale production of propylene from biorenewable resources has become essential. Herein, a new selective route for the synthesis of propylene from bio-derived glycerol is demonstrated. The route consists of the formation of 1-propanol (a versatile bulk chemical) as intermediate through hydrogenolysis of glycerol at a high selectivity. A subsequent dehydration produces propylene. Renewable propylene: Glycerol, which is abundantly available as by-product of biodiesel production, can be efficiently and selectively converted into propylene by using an integrated process involving the formation of 1-propanol as intermediate (see Scheme), thus offering a promising opportunity to meet the growing worldwide propylene demand and supply shortage.

Full text of DOI:10.1002/cssc.201301041

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DOI: 10.1002/cssc.201301041
Propylene from Renewable Resources: Catalytic
Conversion of Glycerol into Propylene
Lei Yu, Jing Yuan, Qi Zhang, Yong-Mei Liu, He-Yong He, Kang-Nian Fan, and Yong Cao*[a]
Propylene, one of the most demanded commodity chemicals,
is obtained overwhelmingly from fossil resources. In view of
the diminishing fossil resources and the ongoing climate
change, the identification of new efficient and alternative
routes for the large-scale production of propylene from biore-
newable resources has become essential. Herein, a new selec-
tive route for the synthesis of propylene from bio-derived glyc-
erol is demonstrated. The route consists of the formation of 1-
propanol (a versatile bulk chemical) as intermediate through
hydrogenolysis of glycerol at a high selectivity. A subsequent
dehydration produces propylene.
relevant methods still very much depend on fossil fuels as the
main raw materials.
Herein, we report the synthesis of on-purpose propylene
using bio-derived glycerol as a renewable feedstock.[7] During
the past decade, glycerol has emerged as a versatile low-cost
bio-feedstock for the production of a variety of value-added
products, essentially because of the large surplus of glycerol
formed as a by-product during the production of biodiesel.[8]
Given its nontoxic and highly functionalized nature, glycerol
represents an ideal raw material with a potential to be convert-
ed into many useful chemicals.[9] The principle challenge in uti-
lizing this particular molecule lies in the development of new,
innovative. and economically feasible catalytic processes that
allow a selective transformation of glycerol to bulk commodity
chemicals on a large scale.[8b] Despite recent significant prog-
ress in developing new processes for converting glycerol into
various low-volume oxygenated chemical compounds,[8,9]
a highly selective route to light olefins,[10] in particular highly
demanded propylene, has remained largely underdeveloped.
As outlined in Scheme 1, our strategy for implementing the
synthesis of propylene from glycerol relies on the formation of
1-propanol (1-PO) as the key intermediate. First, the targeted
With diminishing oil reserves, the production of bulk commod-
ity chemicals will increasingly rely on alternative renewable
feedstocks such as biomass.[1] In this regard, new sustainable
routes to synthesize propylene are of particular interest, as
propylene is one of the most important and widely used com-
modity chemicals derived from petroleum.[2] The primary use
of propylene is for the production of polypropylene, which is
one of the most important thermoplastic resins. The global
polypropylene demand was 26.6 million tonnes in the year
2000 and it is expected to reach 59.6 million tonnes in the year
2020.[3]
Until recently, most propylene produced was a co-product in
ethylene production in steam crackers and a by-product in oil
refineries.[4] With traditional sources of propylene increasingly
unable to meet growing market demands, considerable re-
search efforts have been directed towards the development of
new and greener alternatives for the on-purpose production of
propylene.[5] Examples of such processes include dehydrogena-
tion of propane (PDH), olefin metathesis, methanol to propyl-
ene (MTP), and oxidative dehydrogenation (ODH) of propane.[6]
Of all these processes, PDH has been proven within the last
couple of years to be very effective in producing propylene
on-purpose, offering an economically attractive alternative to
traditional petroleum-based propylene generation.[6g–h] Despite
the great success achieved with on-purpose technologies, all
Scheme 1. Catalytic conversion of glycerol to propylene (GTP).
production of bio-1-PO, a previously unappreciated transfor-
mation for biomass valorization, can be attained through iridi-
um-catalyzed and highly selective hydrogenolysis of glycerol.
By a subsequent dehydration over an acidic H-ZSM-5 zeolite
catalyst, 1-PO can be converted into propylene. Significantly,
propylene can be directly produced in high yields from glycer-
ol by means of a continuous fixed-dual-bed catalytic system.
Details of the development and optimization of this process
are described below.
We began our studies by exploring the hydrogenolysis of
glycerol to 1-PO in aqueous solutions. Although many at-
tempts have been made towards the hydrogenolysis of glycer-
ol to 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-
PDO),[11] the direct conversion of glycerol to 1-PO, a major
commodity chemical currently produced through hydroformy-
lation of ethylene to form propanal followed by hydrogena-
tion,[12] remains essentially unexplored. Our initial investigation
focused on the hydrogenolysis of a diluted aqueous glycerol
[a] L. Yu, J. Yuan, Q. Zhang, Dr. Y.-M. Liu, Prof. Dr. H.-Y. He, Prof. K.-N. Fan,
Prof. Dr. Y. Cao
Department of Chemistry
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials
Fudan University
Handan Road 220, Shanghai 200433 (PR China)
Fax: (+86)21-65643774
E-mail: yongcao@fudan.edu.cn
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201301041.
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Figure 2. Catalytic hydrogenolysis of aqueous glycerol (10 wt%) over 1 wt%
Ir/ZrO2 performed at different temperatures. Reaction conditions: glycerol
&
&
&
1.0 g, Ir/ZrO2 (Ir 0.12 mol%), 4 h, 5 MPa H2 (RT). Selectivity: gas, EtOH,
&
*
1,2-PDO, 1-PO; conversion: glycerol.
5 MPa at 2008C, only a marginal increase of glycerol conver-
sion from 8 to 14% was achieved. Further investigation into
the effect of the reaction temperature at 5 MPa, however, re-
vealed that an increase of temperature from 200 to 2508C dra-
matically boosted glycerol conversion from 14 to 100%
(Figure 2). Note that an even higher selectivity of up to 96%
toward 1-PO formation can be achieved at 2308C. Thus, the
maximum yield of 1-PO can reach up to 94% at 2508C and
5 MPa of H2. This result is remarkable and becomes more rele-
vant for recycling: the catalyst can be reused at least five times
with minimal decrease in both glycerol conversion and selec-
tivity to 1-PO (Figure S2). Of yet further interest is that the spe-
Figure 1. Catalytic hydrogenolysis of aqueous glycerol (10 wt%) over
a) 1 wt% Ir supported on different oxides; and b) various noble metals
loaded on ZrO2. Reaction conditions: glycerol 1.0 g, metal 0.12 mol%,
&
&
&
&
&
2008C, 4 h, 5 MPa H2 (RT). Selectivity: gas, MeOH, EtOH, EG, 1,3-
&
&
*
PDO, 1,2-PDO, 1-PO; conversion: glycerol.
cific activity based on 1-PO formation using the Ir/ZrO2 catalyst
À1
is up to 2.90 molh
g
À1, that is, this catalyst is over 150 times
Ir
(10 wt%) under 5 MPa of H2 at 2008C with iridium supported
on various inorganic oxides as catalysts (Figure 1a). Iridium
was selected because iridium nanoparticles (NPs) and/or com-
plexes are known to catalyze a wide range of organic transfor-
mations including selective hydrogenation and hydrogenoly-
sis.[13] In all cases, 1-PO and 1,2-PDO were formed as the major
products in the liquid phase. All catalysts display an apprecia-
ble or pronounced activity for glycerol conversion, but Ir de-
posited on ZrO2 (Ir/ZrO2) appears to be particularly effective for
the 1-PO formation, with selectivities of up to 90% at 14%
glycerol conversion. The benefit of using Ir as a catalyst be-
comes clear when comparing the activity of Ir/ZrO2 with the
activity of Rh/ZrO2, Pd/ZrO2, Ru/ZrO2, or Pt/ZrO2 (Figure 1b).
Note that previously reported solid catalysts, such as ZrO2-sup-
ported Ru NPs (Ru/ZrO2),[14] showed good activity but inferior
selectivity in terms of 1-PO formation relative to Ir/ZrO2 under
the present reaction conditions.
more active than the previously reported Pt-H2SiW12O40/ZrO2
catalyst (80% selectivity to 1-PO at full glycerol conversion).[12]
To the best of our knowledge, our result represents the first ex-
ample of a heterogeneously catalyzed synthesis of renewable
1-PO by means of an efficient and near quantitative conversion
of bio-derived glycerol.
The outstanding catalytic activity for hydrogenolysis of glyc-
erol over Ir/ZrO2 at the conditions mentioned above clearly re-
flects the fast surface kinetics caused by the intimate interac-
tion of the Ir species with the underlying ZrO2 support. Prelimi-
nary mechanistic analysis of this hydrogenolysis reaction by
monitoring the kinetics of glycerol conversion revealed that
during the whole reaction process 1-PO was always the pri-
mary product (Figure S3), without detecting 1,2-PDO and 1,3-
PDO. Moreover, it was confirmed in two separate experiments
that the formation of 1-PO directly from 1,2-PDO occurred at
a considerably higher rate than that from 1,3-PDO (Table S2),
thus verifying that 1-PO was mainly produced by the formation
of 1,2-PDO as an intermediate during the reaction (Scheme S1).
To better understand the superior performance of Ir/ZrO2, we
characterized the various supports by using NH3-temperature-
programmed desorption (NH3-TPD). ZrO2 shows a greater
abundance of surface acidic sites in comparison to the other
supports (Figure S4). These data, together with the catalytic re-
sults in Figure 1, strongly suggest that the unique bifunctional
As the combination of Ir with zirconia appeared to be essen-
tial for achieving a high catalytic activity for selective 1-PO for-
mation, the next step was to further improve the glycerol con-
version while keeping the undesired formation of 1,2-PDO or
gaseous by-product at its minimum. Using the Ir/ZrO2 catalyst,
we first studied the effect of hydrogen pressure on the hydro-
genolysis of glycerol at 2008C (Figure S1 in the Supporting In-
formation). By increasing the hydrogen pressure from 2 to
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character of the Ir/ZrO2 catalyst is essential to facilitate glycerol
conversion to 1-PO in a highly selective manner.
Table 1. Catalytic performances for hydrogenolysis of aqueous glycerol
with different composition.[a]
A full characterization of the Ir/ZrO2 sample was thus per-
formed, and the following features of this Ir-based catalyst
have been discovered. According to the X-ray absorption near
edge structure (XANES) data (Figure S5), Ir exists only in its
metallic state in the Ir/ZrO2 catalyst. The X-ray diffraction (XRD)
patterns of the Ir/ZrO2 catalyst after reuse revealed that the
crystal phase was similar to that of the fresh Ir/ZrO2 (Figure S6),
and no distinct metallic Ir reflections were visible for both
fresh and used Ir/ZrO2 samples, owing to the fact that the Ir
particle sizes were very small. This scenario can be further cor-
roborated by transmission electron microscopy (TEM) images
of the Ir/ZrO2 catalyst after the reuse, which revealed that the
average diameter (ca. 1.7 nm) and size distribution of the Ir
NPs were similar to those of the fresh Ir/ZrO2 and that no ag-
gregation of the used Ir NPs occurred (Figure S7). By using in-
ductively coupled plasma atomic emission spectroscopy (ICP–
AES) analysis, it was confirmed that there was no leaching of Ir
during the reaction, verifying the inherent stability of the Ir/
ZrO2 catalyst. These results are consistent with the retention of
the catalytic activities of the Ir/ZrO2 catalyst during recycling
experiments.
Entry Feed composition Concentration Conversion Selectivity [%]
[wt%]
[%]
1-PO others[b]
1
2
3
4
5
6
glycerol
glycerol
glycerol
glycerol
crude glycerol[c]
crude glycerol[d]
5
100
100
100
100
100
100
92
94
93
93
94
93
8
6
7
7
6
7
10
30
50
10
10
[a] Reaction conditions: glycerol 1.0 g, catalyst Ir/ZrO2 (Ir 0.12 mol%),
2508C, 4 h, 5 MPa H2 (RT). [b] Others including propane, methane, and
ethanol. [c] Simulated crude glycerol 1.0 g (glycerol/NaCl/methanol at
a mass ratio of 95:4:1). [d] Simulated crude glycerol 1.0 g (glycerol/NaCl/
methanol at a mass ratio of 84:15:1), Ir 0.20 mol%.
carbon source for selective biomass conversion, which may
open the possibility to develop cost-effective and ecofriendly
technologies for the large-scale production of industrial chemi-
cals based on biogenic crude glycerol.
Based on the above results, we next focused on the second
step for the proposed GTP process, that is, the consecutive
conversion of 1-PO to propylene. We initially examined the de-
hydration of neat 1-PO vapors in a vertical fixed-bed reactor
under atmospheric pressure at 2508C with various solid acid
catalysts, including HZSM-5, SAPO-34, MCM-41, and Al2O3
(Table 2). When using the HZSM-5 zeolite, a highly active and
selective catalyst for the dehydration of ethanol,[16] high con-
versions and selectivities were obtained. However, other solid
acid catalysts, such as SAPO-34, MCM-41, or Al2O3, were not ef-
fective for the dehydration of neat 1-PO, producing large
amounts of n-propyl ether as undesired by-product under
identical reaction conditions. Among the various solid acid cat-
alysts examined herein, HZSM5 material with a SiO2/Al2O3
molar ratio of 30 achieves, by far, the best catalytic per-
formance. Notably, by using the HZSM-5-30 sample as catalyst,
Bearing in mind that the water content in crude glycerol can
vary quite significantly depending on different biodiesel pro-
cesses, we have investigated the effect of feedstock concentra-
tion on the Ir-catalyzed hydrogenolysis of glycerol. As shown
in entries 1–4 of Table 1, glycerol with concentrations ranging
from 5–50 wt% can be efficiently converted to 1-PO. It is also
well known that crude glycerol, which is obtained directly
from the bio-diesel industry by transesterification, contains sev-
eral impurities such as methanol (from an incomplete removal
by distillation) and salts (sodium chloride or sodium sulfate
from neutralization of the basic catalysts with HCl or H2SO4).[8a]
As a cost-effective option, it is highly desirable that a less re-
fined glycerol can be directly utilized for downstream applica-
tions. We have thus checked the tolerance of Ir/ZrO2 towards
the possible impurities during the hydrogenolysis of a simulat-
ed crude glycerol. As can be
seen from Table 1, the catalytic
Table 2. Dehydration of 1-PO to produce propylene over various solid acid catalysts.[a]
performance of the Ir/ZrO2
sample in terms of activity and
selectivity did not change with
the addition of NaCl (4 wt%)
and methanol (1 wt%) (entry 5).
In the more challenging reac-
tions uisng simulated crude glyc-
erol with a higher amount of
NaCl (15 wt%) and methanol
(1 wt%) as the reactant, more Ir
catalyst was required to obtain
the desired yield (entry 6).[15]
These results are extremely wel-
come in view of the fact that
crude glycerol with varying
amounts of water and impurities
can be directly used as a viable
Entry
Catalyst
Conversion
[%]
Selectivity [%]
propyl ether
Yield
[%]
propylene
higher hydrocarbon
1
2
3
4
5
6
7
8
9
HZSM-5-30[b]
HZSM-5-60
HZSM-5-100
HZSM-5-200
SAPO-34
MCM-41
Al2O3
HZSM-5-30[c]
HZSM-5-30[d]
>99
96
91
78
35
27
42
>99
>99
>99
99
96
91
82
78
66
>99
>99
trace
trace
trace
trace
18
22
34
trace
trace
trace
>99
95
87
71
29
21
28
>99
>99
1
4
9
–
–
–
trace
trace
[a] Reaction conditions: catalyst 2.0 g, 2508C, neat 1-PO feedstock, weight hourly space velocity WHSV=
1.0 hÀ1, at atmosphere pressure, N2 flow rate 20 mLminÀ1, time on stream 2 h. [b] HZSM-5-X denotes a HZSM-5
zeolite with a SiO2/Al2O3 molar ratio of X. [c] 10 wt% aqueous 1-PO solution. [d] 50 wt% aqueous 1-PO
solution.
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neat 1-PO can be quantitatively converted into propylene. To
investigate the intrinsic reason for different catalytic perform-
ances, we characterized the various solid acid catalysts by
using NH3-temperatue-programmed desorption (NH3-TPD). Ac-
cording to Figure S9, all catalysts showed two peaks, clearly in-
dicating the presence of both weak and medium strong acidic
sites. Importantly, it is revealed that the HZSM-5-30 sample has
more weak acidic sites than medium strong acidic sites in com-
parison to other materials. Combining the results from the ac-
tivity tests and NH3-TPD, it is likely that the dehydration of 1-
PO proceeds effectively in the presence of solid acid catalysts
because of the presence of a higher population of weak acidic
sites.
Thus far, a stepwise approach to synthesize propylene using
glycerol as a renewable feedstock has been outlined. From
a process integration point of view, the efficiency and utility of
this sequence could be improved if a direct continuous pro-
cess that combines the conversion of glycerol to 1-PO coupled
with a consecutive dehydration step could be implemented.
In a related study, Sousa Fadigas et al.[18] described in a recent
patent that the direct conversion of glycerol to propylene can
be achieved by using a complex multi-metallic catalyst com-
posed of Fe–Mo mixed oxides supported on activated carbon.
However, issues such as poor long-term performance of the
catalyst and unsolved reaction pathway remain of concern.
We have performed a similar direct conversion of glycerol into
propylene under relatively mild conditions (2508C, 5 MPa) by
combining Ir/ZrO2 with a 1-PO dehydration catalyst in a fixed-
dual-bed reactor (Scheme S2). Nevertheless, preliminary experi-
ments with the fixed-dual-bed reactor showed that the yield of
propylene from glycerol conversion was significantly lower
than expected: only 67% of propylene was detected (Table 3,
Given the observed high dehydration activity, more relevant
studies have been performed to simulate the H2O-containing
feed produced from the aqueous glycerol hydrogenolysis pro-
cess described above (Table 2). The diluted aqueous 1-PO
vapors were readily dehydrated to propylene with high yield
in aqueous solution at different 1-PO concentrations (10 and
50 wt%, respectively). Rapid deactivation represents a serious
problem for HZSM-5 zeolite-catalyzed alcohol dehydrations be-
cause of its low anticoking ability.[17] To examine the likely sta-
bility of HZSM-5-30 for the dehydration of aqueous 1-PO to
propylene, we investigated the long-term performance. In our
catalytic system, no deactivation was observed for up to 50 h
on stream. However, the conversion of 1-PO decayed rapidly
after 50 h and regeneration, therefore, seems crucial for practi-
cal applications. Note that such deactivation could be largely
ascribed to the blocking of the active acid sites by carbon dep-
osition as revealed by thermogravimetric analysis (Figure S10).
For regeneration of the deactivated HZSM-5-30 after 60 h on
steam, the reaction was interrupted under an N2 steam, and
then air was introduced at 5008C to burn off carbon species
deposited on the catalyst. After the first and second regenera-
tion, a high yield of propylene (over 99%) could be achieved
again (Figure 3). To the best of our knowledge, such superior
catalytic performance has to date never been achieved in the
selective conversion of bio-derived 1-PO to propylene.
Table 3. Direct conversion of glycerol into propylene over Ir/ZrO2 cou-
pled with HZSM-5-30.[a]
Entry
Catalyst
PH
[MPa]
Conversion
[%]
Selectivity
[%]
2
1[b]
2[b]
3[b]
4[b]
5[c]
6[d]
Ir/ZrO2&HZSM-5-30
Ir/ZrO2&HZSM-5-30
Ir/ZrO2&HZSM-5-30
Ir/ZrO2&HZSM-5-30
Ir/ZrO2
5
3
1
0.5
1
100
100
100
73
100
21
67
79
85
88
5
HZSM-5-30
1
–
[a] Reaction conditions: Ir/ZrO2 2.0 g, HZSM-5-30 2.0 g, 2508C, 30 wt%
aqueous glycerol, WHSV=1.0 hÀ1, H2/glycerol=100 (molar ratio), time on
stream 2 h. [b] The main by-product was propane. [c] The main by-prod-
uct was 1-PO. [d] The main by-product was acrolein.
entry 1). To suppress the undesirable formation of propane
during the reaction, we thus decided to decrease the hydro-
gen pressure used for the continuous flow reaction. Thus, it is
possible to achieve a high propylene yield of up to 85% by de-
creasing the hydrogen pressure from 5 to 1 MPa (entries 2–4).
Importantly, under the conditions in entry 3 of Table 3, no sig-
nificant decreases in glycerol conversion and propylene selec-
tivity occurred within 40 h, and the propylene yield could be
maintained at about 85% (Figure S11). The results, while pre-
liminary, are encouraging. From a practical perspective, future
research should focus on a full optimization of the reaction pa-
rameters as well as a further screening of dual catalyst systems
for the selective production of propylene by means of a direct
conversion of glycerol.
In summary, we have demonstrated a selective route for the
synthesis of propylene using biorenewable glycerol as reliable
and cost-effective feedstock. The route features the formation
of 1-PO as intermediate through hydrogenolysis of glycerol,
which was achieved with an unprecedented high selectivity.
Figure 3. Long-term performance of dehydration of aqueous 1-PO (50 wt%)
over HZSM-5-30. Reaction conditions: 2.0 g HZSM-5-30, 2508C, 50 wt%
aqueous 1-PO feedstock, WHSV=1.0 hÀ1, at atmosphere pressure, N2 flow
rate 20 mLminÀ1, selectivity to propylene always >99%.
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Experimental Section
General procedure for the hydrogenolysis of glycerol to 1-PO:
A mixture of glycerol (1.0 g), catalysts (metal 0.12 mol%), 2-me-
thoxyethyl ether (2 mmol, internal standard), and water (9 mL)
were charged into a 100 mL Hastelloy-C high pressure Parr reactor
and stirred at a rate of 800 rpm under 5 MPa H2 for a given reac-
tion time. The products were analyzed by using a gas chromato-
graph. The identification of the products was performed by using
a GC–MS spectrometer. The conversion and the selectivity were de-
fined on the carbon basis. See the Supporting Information for the
experimental details
General procedure for the dehydration of 1-PO to propylene:
The dehydration of 1-PO was performed in a vertical fixed-bed re-
actor (inner diameter 10 mm, length 500 mm) under atmospheric
pressure at 2508C. The catalyst (2.0 g) was placed in the middle of
a stainless reactor. The 1-PO feedstock was continuously intro-
duced into the reactor by means of an HPLC pump at a WHSV of
1.0 hÀ1. The products were obtained when the reaction reached
steady state. Then, the liquid and gas products were cooled, col-
lected in a gas–liquid separator and analyzed by using a gas chro-
matograph.
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This work was support by National Natural Science Foundation
of China (21073042, 21273044), the State Key Basic Research Pro-
gram of PRC (2009CB623506), the Research Fund for the Doctoral
Program of Higher Education (2012007000011) and Science&-
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Keywords: biomass · dehydration · glycerol · hydrogenolysis ·
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