Aqueous phase hydrogenation of levulinic acid to 1,4-pentanediol

Article abstract of DOI:10.1039/c3cc48236g

For the first time, Mo modified Rh/SiO₂ was found to be an effective catalyst for the aqueous phase selective hydrogenation of levulinic acid to 1,4-pentanediol. Over such a catalyst, high levulinic acid conversion (100%) and 1,4-pentanediol yield (70%) can be achieved at low temperature (353 K). This journal is The Royal Society of Chemistry.

Full text of DOI:10.1039/c3cc48236g

Showcasing research from Ning Li’s Laboratory/State Key
Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian, China
As featured in:
Aqueous phase hydrogenation of levulinic acid to
1,4-pentanediol
Mo-modified Rh/SiO was first reported to be effective for the
2
aqueous-phase selective hydrogenation of levulinic acid to
1
(
,4-pentanediol. Over this catalyst, high levulinic acid conversion
100%) and 1,4-pentanediol yield (70%) can be achieved at low
temperature (353 K).
See Ning Li et al.,
Chem. Commun., 2014, 50, 1414.
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Aqueous phase hydrogenation of levulinic acid to
,4-pentanediol†
1
Cite this: Chem. Commun., 2014,
0, 1414
5
ab
ac
a
a
b
Mengxia Li,‡ Guangyi Li,‡ Ning Li,* Aiqin Wang, Wenjun Dong,*
a
a
Received 28th October 2013,
Accepted 2nd December 2013
Xiaodong Wang and Yu Cong
DOI: 10.1039/c3cc48236g
www.rsc.org/chemcomm
For the first time, Mo modified Rh/SiO was found to be an effective directly used as fuel without hydrotreating. In some reports in
2
1
3
catalyst for the aqueous phase selective hydrogenation of levulinic the literature, the hydrogenation of carboxylic acids was
acid to 1,4-pentanediol. Over such a catalyst, high levulinic acid considered to be one of the slowest steps in the hydrotreatment
conversion (100%) and 1,4-pentanediol yield (70%) can be achieved of bio-oils. To fulfill the need for a real application, more
at low temperature (353 K).
effective catalysts should be developed.
Levulinic acid is a very important platform chemical which can
14,15
With the increasing social concern about the energy and be produced by the chemical treatment of lignocellulose.
As
environmental problems, the catalytic conversion of renewable the product of the simultaneous hydrogenation of the carbonyl
1
,2
3,4
biomass to fuel and chemicals has drawn a lot of attention. and carboxyl groups in levulinic acid, 1,4-pentanediol can be used
4,16
Carboxylic acids are a family of chemicals which can be as a potential monomer for the production of polyesters.
produced by the biological and chemical treatment of biomass. However, due to the preferable intermolecular esterification, most
The selective hydrogenation of carboxylic acids to their corre- of the research regarding the hydrogenation of levulinic acid was
1
6,17
sponding alcohols or diols is a very important reaction in the focused on its conversion to g-valerolactone (GVL)
which
1
8
biomass refinery. For example, the selective hydrogenation of can be used as fuel additive or feedstock for biojet fuels. For
acetic acid, propanoic acid, lactic acid and succinic acid from the selective hydrogenation of levulinic acid to 1,4-pentanediol,
5
6
the fermentation of biomass can produce ethanol, propanol,
only homogenous organometallic catalysts based on Ru(acac)
3
7
8–10
19–21
1,2-propanediol and 1,4-butanediol.
These compounds can and a triphos ligand have been reported.
This system has
be used as biofuel or as monomers for the production of drawbacks of non-reusability, special handling of metal complexes
22
polyesters. Secondly, the selective hydrogenation of fatty acids and the high cost of phosphine ligands. As a solution, Cao et al.
from the hydrolysis of triglycerides can produce fatty alcohols found that 1,4-pentanediol can be produced by the selective
which are widely used in lubricants, non-ionic surfactants, hydrogenation of GVL over a copper zirconia catalyst. To the
1
1,12
perfumes, resins, cosmetics, and conditioners.
application, the selective hydrogenation can be used for the selective hydrogenation of levulinic acid to 1,4-pentanediol over
removal of carboxylic acids in the bio-oil from the pyrolysis or a heterogeneous catalyst. In this work, a Mo modified Rh/SiO
liquefaction of biomass. These acids increase the acid value of (Rh–MoO /SiO ) catalyst was first used for the aqueous phase
As the third best of our knowledge, there is no report about the direct
2
x
2
bio-oil and make it corrosive. As a result, the bio-oil cannot be hydrogenation of levulinic acid and exhibited high selectivity to
,4-pentanediol at low temperature (353 K). The reaction path-
way and the reason for the promotion effect of Mo were explored.
The possibility of using the Rh–MoO /SiO catalyst for the
1
a
b
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian 116023, China. E-mail: lining@dicp.ac.cn;
Fax: +86-411-84691570; Tel: +86-411-84379738
x
2
aqueous phase selective hydrogenation of other biomass derived
carboxylic acids was also investigated.
Center for Optoelectronics Materials and Devices, College of Science,
Zhejiang Sci-Tech University, Hangzhou 310018, China.
From the results shown in Table 1, we can see that the Rh/SiO
2
E-mail: wenjundong@zstu.edu.cn; Tel: +86-571-86843587
catalyst is very active for the aqueous phase hydrogenation of
levulinic acid. Under the investigated conditions (353 K, 6 MPa),
the levulinic acid is completely converted with GVL as the major
product. The yield of 1,4-pentanediol in the liquid product was
very low (1%). After modification with a small amount of Mo, the
c
Graduate University of Chinese Academy of Sciences, Beijing 10049, China
Electronic supplementary information (ESI) available: Detailed information
†
about preparation and characterization of catalysts, activity test, the experimental
results for the analysis of gas phase products and the stability of Rh–MoO
catalyst. See DOI: 10.1039/c3cc48236g
x 2
/SiO
‡
These authors contributed equally to this work.
2
levulinic acid conversion over the Rh/SiO catalyst was unchanged
1
414 | Chem. Commun., 2014, 50, 1414--1416
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Table 1 Results for the hydrogenation of levulinic acid or GVL over different catalysts. Reaction conditions: 353 K, 6 MPa, 2.0 g catalyst, 10% levulinic
À1
À1
acid (or GVL) aqueous solution flow rate 0.08 mL min , H
2
flow rate 60 mL min
a
Selectivity (%)
Mo/M atomic ratio
(M: Rh, Ir, Pt, Pd, Ru)
Conversion of levulinic
acid or GVL (%)
Entry
Catalyst
1,4-PeD
2-Peol
1-Peol
GVL
MTHF
Others
1
2
3
4
5
6
7
8
9
1
1
1
1
1
4%Rh/SiO
2
0
100
100
100
100
100
1.5
100
100
100
100
100
100
86.2
68.2
1.2
45.3
70.0
65.2
38.5
0
0.4
8.9
13.2
5.8
3.4
0
0.4
15.1
0.8
1.6
0
0
76.8
34.9
1.1
20.2
24.5
0
80.8
18.0
56.8
79.2
77.2
58.1
87.5
—
0.1
2.0
4.7
1.3
1.7
0
0.2
0.4
0.0
2.5
0.5
1.9
0.5
5.5
21.5
3.7
8.4
4%Rh–MoO
4%Rh–MoO
4%Rh–MoO
4%Rh–MoO
x
x
x
x
/SiO
/SiO
/SiO
/SiO
2
2
2
2
0.07
0.13
0.25
0.50
—
0.13
0.13
0.13
0.13
0.13
0.13
0.13
0.13
5.2
2.6
0.7
0.3
0
0.1
0.3
0.2
0
0.1
1.7
0.5
4.7
6.7
31.5
100
16.9
13.2
28.9
0.9
21.9
1.1
1.1
MoO
4%Rh/SiO
4%Ir–MoO
4%Pt–MoO
4%Ru–MoO
4%Pd–MoO
x
/SiO
2
b
2
2
+ MoO
/SiO
/SiO
x
/SiO
1.8
x
2
52.9
13.3
15.8
0.3
28.3
7.8
x
2
0
1
2
3
4
x
/SiO
2
x
/SiO
2
c
4%Rh–MoO
4%Rh–MoO
4%Rh–MoO
x
x
x
/SiO
/SiO
/SiO
2
2
2
8.9
2.6
9.0
c
d
61.8
19.0
a
1
,4-PeD = 1,4-pentanediol; 2-peol = 2-pentanol; 1-peol = 1-pentanol; GVL = g-valerolactone; MTHF = 2-methyl-tetrahydrofuran; others means
b
alkanes and some unidentified products (detailed information is provided in Table S1 of ESI). 4%Rh/SiO
2
+ MoO
at the mass ratio of 1 : 1. Experiment 12 and 13 were carried out with 0.5 g and 0.2 g 4%Rh–MoO
Mo/Rh = 0.13) catalyst, respectively. Experiment 14 was carried out with 10% GVL aqueous solution.
x
/SiO
2
means the physical
c
mixture of the 4%Rh/SiO
(
2
and MoO
x
/SdiO
2
x
/SiO
2
but the main hydrogenation product shifted from GVL to catalyst (see entry 14 in Table 1). It was found that GVL can be
,4-pentanediol. The promotion effect of Mo was most evident converted to 1,4-pentanediol over the Rh–MoO /SiO catalyst
when the Mo/Rh atomic ratio was between 0.13 and 0.25. under similar conditions. As suggested in the literature,
Further increase of Mo/Rh atomic ratio led to the decrease of GVL may be a possible intermediate for the hydrogenation of
selectivity towards 1,4-pentanediol and the increase of the GVL levulinic acid to 1,4-pentanediol over the Rh–MoO /SiO catalyst.
yield. Moreover, we also studied the catalytic performances of To find out the intrinsic reason for the excellent performance
MoO /SiO and its physical mixture with Rh/SiO . To facilitate of the Rh–MoO /SiO catalyst in the selective hydrogenation of
1
x
2
1
9,21
x
2
x
2
2
x
2
the comparison, the Rh and/or Mo content in these catalysts levulinic acid to 1,4-pentanediol, we compared the activities of
were kept the same as the ones in 4%Rh–MoO /SiO (Mo/Rh = Rh/SiO and Rh–MoO /SiO for the aqueous phase hydrogenation
.13). As shown in Table 1, the MoO /SiO catalyst is inactive for the of carboxyl group using acetic acid as the model compound. From
hydrogenation of levulinic acid, while the catalytic performance of Fig. 1, the Rh/SiO is inactive for the hydrogenation of acetic acid
the physical mixture of Rh/SiO and MoO /SiO is almost the same under the investigated conditions. This result is consistent with the
as that of Rh/SiO . From these results, the excellent catalytic previous work of Huber group. In contrast, higher acetic acid
performance of Rh–MoO /SiO for the hydrogenation of levulinic conversion (100%) and ethanol yield (83%) can be achieved over
x
2
2
x
2
0
x
2
2
2
x
2
5
2
x
2
acid can be explained by the synergy effect between the closely Rh–MoO /SiO . From this result, we can see that the modification of
x
2
contacting Rh and Mo species.
The performances of various Mo modified noble metal catalyst, which may be the reason for the higher selectivity of the
M–MoO /SiO , M = Rh, Ir, Pt, Ru, Pd) catalysts in the aqueous
phase hydrogenation of levulinic acid were compared (entries 3,
–11 in Table 1). Among these catalysts, Rh–MoO /SiO exhibited
the highest selectivity to 1,4-pentanediol. Besides Rh–MoO
SiO , the Ir–MoO /SiO catalyst was also selective for the hydro-
Mo promoted the hydrogenation of carboxyl group over the Rh
(
x
2
8
x
2
x
/
2
x
2
genation of levulinic acid to 1,4-pentanediol, but the selectivity
to 1,4-pentanediol over this catalyst is slightly lower than that of
Rh–MoO
selectivity to 1,4-pentanediol. In contrast, Pd–MoO
totally unselective for the production of 1,4-pentanediol.
The reaction pathway for the conversion of levulinic acid to
,4-pentanediol over Rh–MoO /SiO was explored. With the
x
/SiO
2
. Pt–MoO
x
/SiO
2
and Ru–MoO
x
/SiO
2
have lower
x
/SiO is
2
1
x
2
decrease of catalyst loading (see entries 3, 12 and 13 in
Table 1), the main product from the hydrogenation of levulinic
acid over the 4%Rh–MoO /SiO (Mo/Rh = 0.13) catalyst shifted
x 2
from 1,4-pentanediol to GVL. This phenomenon is more evident
at lower catalyst loading. Moreover, we also investigated the
Fig. 1 Hydrogenation of acetic acid over 4%Rh/SiO
2 x 2
and 4%Rh–MoO /SiO
(
Mo/Rh = 0.13). Reaction conditions: 353 K, 6 MPa, 2.0 g catalyst, 10% acetic
À1
À1
.
aqueous phase hydrogenation of GVL over the Rh–MoO
x
/SiO
2
acid aqueous solution flow rate: 0.08 mL min , H
2
flow rate: 60 mL min
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Table 2 Results for the hydrogenation of different biomass derived of 1,4-pentanediol over the Rh–MoO
/SiO
catalyst. From the
x
2
carboxylic acids over the 4%Rh–MoO
x 2
/SiO (Mo/Rh = 0.13). Reaction
reactions of some model compounds, it was found that the
modification of Mo promoted the hydrogenation of the carboxyl
group over the Rh/SiO catalyst, which was responsible for the
conditions: 353 K, 6 MPa, 2.0 g catalyst, 10% carboxylic acid aqueous
À1
À1
solutions flow rate 0.08 mL min , H
2
flow rate 60 mL min
2
Reactant
Conversion (%)
100
Product
Selectivity (%) higher selectivity of 1,4-pentanediol over the Rh–MoO /SiO2
x
catalyst.
This work was supported by the Natural Science Foundation
Propanoic acid
Propanol
76.2
a
Others
23.8
68.4
31.6
58.8
14.2
27.0
46.1
13.9
40.0
42.0
17.4
40.6
Butanoic acid
Lactic acid
100
Butanol
a
of China (No. 21106143; No. 21277140), 100-talent project of
Dalian Institute of Chemical Physics (DICP) Zhejiang Provincial
Natural Science Foundation of China (LR12E02001), and the
Independent Innovation Foundation of State Key Laboratory of
Catalysis (No. R201113) of DICP.
Others
76.9
1,2-Propanediol
1
-Propanol
a
Others
Malonic acid
96.2
99.0
1,3-Propanediol
1
-Propanol
a
Others
b
Succinic acid
1,4-Butanediol
Notes and references
1
-Butanol
a
Others
1
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a
Others means light alkanes and some unidentified products (see
4044–4098.
b
Table S2 of ESI). 5% aqueous solution of succinic acid was used as
feedstock.
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1
1
1
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1
1
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1
1
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5510–5514.
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catalyst for future applications.
x 2
Mo modified Rh/SiO (Rh–MoO /SiO ) is a promising catalyst
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2
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1
416 | Chem. Commun., 2014, 50, 1414--1416
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