Direct conversion of carbohydrates to γ-valerolactone facilitated by a solvent effect

Article abstract of DOI:10.1039/c5gc00110b

The carbohydrates (cellulose, starch, inulin, maltose, sucrose, glucose and fructose) were converted efficiently into γ-valerolactone (GVL) over combined H₃PW₁₂O₄₀ and Ru/TiO₂ catalysts under mild conditions. The basicity of oxygen-containing solvents had a remarkable effect on the acid strength of H₃PW₁₂O₄₀, which resulted in great variation in the yield of GVL. H₃PW₁₂O₄₀ was more effective in 20 vol% water/γ-butyrolactone than in pure water and other water/organic solvents (methanol, ethanol and 1,4-dioxane). GVL yields for inulin and fructose reached 70.5 mol% and 67.6 mol% respectively. Meanwhile, a GVL yield of 40.5 mol% was achieved for cellulose. In addition, a practical method for catalyst recycling and GVL separation was developed by adding sugar into the reaction mixture. H₃PW₁₂O₄₀ and Ru/TiO₂ maintained their activity after three recycling runs.

Full text of DOI:10.1039/c5gc00110b

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Direct conversion of carbohydrates to γꢀvalerolactone
facilitated by solvent effect
Cite this: DOI: 10.1039/x0xx00000x
Jinglei Cui,ab Jingjing Tan,ab Tiansheng Deng,a Xiaojing Cui,a Hongyan Zheng,c Yulei
ac
Zhu*ac and Yongwang Li
Received 00th January 2012,
Accepted 00th January 2012
The carbohydrates (cellulose, starch, inulin, maltose, sucrose, glucose and fructose) were
converted efficiently into γꢀvalerolactone (GVL) over combined H3PW12O40 and Ru/TiO2
catalysts under mild conditions. The basicity of oxygenꢀcontaining solvents had a remarkable
effect on the acid strength of H3PW12O40, which resulted in a great variation in the yield of
GVL. H3PW12O40 was more effective in 20 vol% water/γꢀbutyrolactone than in pure water and
other water/organic solvents (methanol, ethanol and 1,4ꢀdioxane). GVL yields for inulin and
fructose reached 70.5 mol% and 67.6 mol% respectively. Meanwhile, a GVL yield of 40.5
mol% was achieved for cellulose. Besides, a practical method for catalyst recycling and GVL
separation was developed by adding sugar into the reaction mixture. H3PW12O40 and Ru/TiO2
maintained its activity after three recycling runs.
DOI: 10.1039/x0xx00000x
www.rsc.org/
efforts have been focused on the direct production of GVL from
carbohydrates, predominantly from fructose and glucose. Both
Brønsted acid catalyst and hydrogenation catalyst were required for
Introduction
The diminishing of fossil resource promotes the development of
alternative energy sources and green chemicals for society.1 Biofuels
are promising replacements as they are produced from renewable
biomass materials, particularly from the most abundant biomassꢀ
derived sugars. With feasible catalytic processes, a variety of
platform compounds can be produced from sugars, among which γꢀ
valerolactone (GVL) is an appealing platform molecule.2,3 GVL can
be applied directly as fuel additives.4 It is also considered as an
outstanding raw material for production of biofuels and fine
chemicals, including 2ꢀMethyltetrahydrofuran (2ꢀMeTHF), 1, 4ꢀ
pentanediols, highꢀgrade liquid alkene fuels and polymers.5ꢀ7
the conversion of carbohydrates into GVL in the oneꢀstep method.15
Heeres et al. investigated oneꢀstep conversion of fructose and
glucose to GVL over combined Ru/C and trifluoroacetic acid
catalyst.16 Braca et al. used combined Ruꢀcarbonyls (Ru(CO)4I2) and
HI catalyst for the conversion of Dꢀglucose and Dꢀfructose to GVL,
and GVL yield reached 40 mol% at 200 oC.17 It is desirable but more
challenging to obtain a high GVL yield at milder conditions.
Recently, the direct conversion of fructose to GVL with a moderate
o
yield of 55 mol% was achieved at a low temperature (130 C) in
GVL (solvent) over combined H2SO4 and a Shvoꢀcatalyst.18 As
promising renewable sources that are rich in nature, polysaccharides,
particularly cellulose, are more attractive raw materials than glucose
and fructose for producing GVL. However, the oneꢀstep production
of GVL from cellulose was seldom reported. The current technology
for synthesis of GVL from cellulose contains multiꢀstep processes, in
which cellulose is converted into LA on strong acid catalysts at high
temperatures and subsequent hydrogenation to give GVL.19ꢀ21 For
example, LA was produced from cellulose in GVL/water mixture,
followed by an efficient hydrogenation of upstream solutions at 220
oC.20 In the work of Ding et al., the conversion of cellulose to LA
Oneꢀstep strategy
OH
OH
OH
O
OH
O
OH
OH
O
+
HO
OH
+
O
H O/ H
2
H
2
H O/ H
2
O
HO
OH
HO
O
O
OH
metal catalyst
O
HO
HO
O
OH
n
OH
OH
polysaccharide
monosaccharide
γꢀvalerolactone
levulinic acid
Scheme 1 Reaction pathways from carbohydrates to GVL
o
was catalyzed by a heterogeneous acid catalyst at 180 C, and LA
was further converted to GVL on a Ru/C catalyst.21
The primary method for GVL production from carbohydrates is
Hence, it is demanding to develop a more efficient and greener
process for direct production of GVL from carbohydrates, particular
from cellulose. The design of a robust Brønsted acid catalyst is
primary for this goal.22,23 The acidity of Brønsted acid catalysts is
not only determined by its intrinsic nature, but also dependent on
solvent. Solvents, particularly waterꢀcontained solvents that are
common in the conversion process of biomass, usually affect the
acidity of Brønsted acid catalysts.24 Protons of Brønsted acid catalyst
are readily to interact with oxygen atom of H2O to form H3O+ ions.
In other words, the basicity of oxygen atom of H2O weakens the
based on an integrated technology consisting of the transformation
of carbohydrates to levulinic acid (LA) with acid catalysts and
subsequent hydrogenation to GVL in the presence of a metal catalyst
(see scheme 1).8ꢀ10 Commercial production of LA is generally
performed in waterꢀcontained medium,11 and an energyꢀintensive
separation of LA or its esters from the waterꢀcontained upstream is
required before the following hydrogenation process.12,13 In contrast,
oneꢀstep conversion of carbohydrates to GVL is more economical as
separation of LA is not necessary.14
In view of the advantages of oneꢀstep strategy, a few of pioneer
This journal is © The Royal Society of Chemistry 2013
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Green Chemistry
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VJieowuArrtnicalelONnlainme e
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DOI: 10.1039/C5GC00110B
acidity of Brønsted acid catalysts. This has been demonstrated to is much less expensive commodity which has extremely similar
lower obviously the catalytic efficiency of Brønsted acid catalysts.25 physicochemical properties to GVL. More importantly, the basicity
Therefore, solvents that are more beneficial for the efficiency of acid of GBL, namely the basicity of oxygen atom of GBL, is weaker than
catalysts than water are necessary. Furthermore, a highly active
metal catalyst that is resistance to acid is required to convert the
Table 1 Direct conversion of fructose to GVL in various solvents a
formed LA to GVL efficiently.26ꢀ28 Our latest research discovered
that supported Ru/TiO2 catalyst owned a high efficiency for catalytic
Entry
1b
solvent
Water
HPA/g
0.4
GVL yield/mol%
27.5
hydrogenation of LA and an excellent stability in the concentrated
acid/water solution.29
Herein, combined catalysts consisted of a strong Brønsted acid
H3PW12O40 (HPA) and Ru/TiO2 are reported in this paper to produce
GVL efficiently from carbohydrates (cellulose, inulin, starch,
sucrose, maltose, glucose and fructose) via a single step in a
monophasic γꢀbutyrolactone/water solvent under a mild reaction
condition. The solvent effect on the acidity of H3PW12O40 and
further on the catalytic behaviors of H3PW12O40 was investigated. In
comparison with pure water, organic/water solvents, particularly
GBL/water solvent, promoted drastically the catalytic efficiency of
HPA. GVL yields reached 70.5 mol % and 67.6 mol% from inulin
2
3
Water
0.4
0.4
0.4
0.1
0.2
0.4
0.6
0.8
0.1
0.2
0.4
0.6
0.8
trace
15.7
21.8
17.5
27.3
40.3
41.5
41.9
42.3
51.5
58.9
57.6
55.7
Methanol/water
Ethanol/water
1,4ꢀdioxane/water
1,4ꢀdioxane/water
1,4ꢀdioxane/water
1,4ꢀdioxane/water
1,4ꢀdioxane/water
GBL/water
4
5
6
o
and fructose at 130ꢀ150 C and 4 MPa, respectively. Moreover, a
7
GVL yield of 40.5 mol% was achieved by direct conversion of
cellulose. Furthermore, a practical method was developed for GVL
separation and catalysts recycling, and more than 60 mol% yield of
GVL was obtained from fructose on HPAꢀRu/TiO2 catalysts after
three recycling runs.
8
9
10
11
12
13
14
Results and discussion
GBL/water
GBL/water
Combined HPA and Ru/TiO2 catalysts were applied to produce GVL
from fructose. Initially, the reaction was performed in water (Table 1,
entries 1, 2 ,Table S1 and S2 in ESI†). Both GVL and LA were
detected in the reaction. Noticeably, a large amount of insoluble
humin was observed in the reaction mixture after the reaction.
Humin is usually reported to be produced from the polymerization of
fructose and its dehydration intermediates such as HMF.30 The low
GVL yield implied that the conversion of fructose to LA in water
was insufficient. Both reaction rate and product distribution are
sensitive to the acid concentration for the conversion of fructose to
LA.31 It was therefore assumed that the insufficient conversion of
fructose to LA may stem from the deficiency in the amount of acid
sites. The amount of HPA in the reactions was increased. The
resulting enhancement in the GVL yield implied a promotion in the
conversion of fructose to LA (Table S2, ESI†). However, the highest
GVL yield was no more than 42 mol% with a large amount of HPA.
HPA itself is a strong Brønsted acid, and its acid strength is much
stronger than 98 wt% H2SO4 aqueous solution.32 It is likely that HPA
can catalyze the conversion of carbohydrates into LA at a milder
condition than liquid acids such as H2SO4 and HI. Hence, the low
catalytic efficiency of HPA is more likely attributed to the fact that
the acid strength of HPA was weakened by water, for oxygen atom
of H2O acts as a Brønsted alkali.33 To improve the catalytic
GBL/water
GBL/water
a: 1 g Dꢀfructose, 130 oC, H2, 4 MPa, 0.2 g 2 wt% Ru/TiO2,
reaction time 10 h, 20 ml of solvent, 20 v/v% of water
content in organic/water mixtures, no LA and fructose were
detected; b: 180 oC; c: the characterizations of Ru/TiO2
were shown in supporting information (Figure S1, S2, S3
and Table S3).
water. The weak basicity of GBL would bring less damage on the
acidity of HPA. Hence, GBL was selected as the reaction medium in
this study. A higher GVL yield was obtained in GBL/water than that
in other organic counterparts (Table 1, entries 10ꢀ14), indicating the
excellent ability of GBL/water for enhancing the catalyst efficiency.
The yield of GVL reached the highest level when HPA amount was
0.4 g in GBL/water mixture. Moreover, a faster reaction rate for
fructose to GVL was observed in GBL/water than in pure water, and
the reaction was completed within 6 hours in GBL/water mixture
(Figure S4, ESI†). GVL was the main liquid product (Table S5, ESI†)
efficiency of HPA, it is of vital importance to maintain the acid in GBL/water reaction system, and the mass balance was no more
than 70 %. The reaction mixture was transparent and its colour was
bright yellow after the reaction (Figure S6b, ESI†). This indicated
the absence of insoluble humins in the reaction solution. The carbon
content in the used Ru/TiO2 catalyst was analyzed, and trace amount
of carbon was detected. These results suggested that insoluble
strength of HPA. Solvents with weaker basicity than water would
favor the preservation of acid strength of HPA. Based on this
acknowledgement, several oxygenꢀcontained organic agent including
methanol, ethanol and 1, 4ꢀdioxane were selected as the solvent.
Indeed, higher GVL yields were obtained in these three organic
agent/water mixtures at a much lower reaction temperature than pure
water (Table 1, entries 3ꢀ9).
γꢀlactones, particularly GVL, are excellent solvents for the acid
catalytic conversion of sugars for their stable and nonꢀtoxic nature.25
However, it is inevitable to consume a substantial valuable GVL in
the process using GVL as solvent. In contrast, γꢀbutyrolactone (GBL)
humins was not formed in the reaction.
Additionally, the
+
composition of gas product was analyzed during the reaction. C2
alkanes, CO and CO2 were not found, and only trace amount of CH4
was detected. Therefore, soluble humins that formed in the reaction
was deduced to account for the majority of missing mass balance.
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5GC00110B
Water is essential for the conversion of fructose to GVL, despite it
is unfavorable for the catalytic efficiency of HPA. Water is required
to dissolve fructose, and it acts as a reactant in the process of
fructose to LA. Water was identified in this work to accelerate the
hydrogenation of LA to GVL, in comparison with organic solvents
(Figure S5, ESI†). Therefore, the effect of water content in solvent
on GVL yield was investigated. Solvent with a water content of 10 to
20 vol% facilitated GVL formation, whereas a drastic decline of
GVL yield was observed as the water content exceeded 30 vol%
(Table 2, entries 1ꢀ6). With excess water in solvent, the efficiency of
HPA catalyst was greatly reduced and the degradation of fructose
and its intermediates to humin were promoted, resulting in a low
GVL yield.3b The effect of total amount of GBL/water solvent on
GVL yield was also studied (Table 2, entries 7ꢀ10). A stepwise
increment of GVL yield was observed as the solvent volume
decreased from 30 ml to 10 ml. As the amount of solvent reduced to
5 ml, a drastic decline in GVL yield occurred due to a high
concentration of substrate promoted the formation of humin.3b
Moreover, the effects of other reaction parameters including reaction
temperature and H2 pressure were investigated (Table 3). The
increasing of temperature and pressure enhanced GVL yield. The
highest GVL yield of 67.6 mol% was obtained at 130 oC and 4 MPa.
In comparison, the highest yield of GVL in the literature was 62
mol%, which was obtained at more severe conditions (180 oC and 94
bar H2).16 The above result indicated that the combined HPAꢀ
Ru/TiO2 catalysts in GBL/water showed a great capability in
producing GVL from fructose efficiently.
Table 3 The effect of reaction temperature and H2 pressure a
Entry Temperature/oC H2 pressure/MPa
GVL
yield/mol%
1
2
3
4
5
6
7
8
120
140
150
160
130
130
130
130
4
4
4
4
2
3
4
5
45.6
67.1
67.5
67.8
37.9
50.1
67.6
67.8
a: 1 g Dꢀfructose, reaction time 6 h, 0.4 g HPA, 0.2 g 2 wt%
Ru/TiO2, 10 ml 20 vol% water/GBL as solvent, no fructose or
LA was detected after the reaction in all experiment runs.
the above mentioned monophasic reaction mixture, it would
preferentially coordinate with water. The monophasic reaction
mixture in such case would separate into two phases, namely, the top
layer containing GVL and the bottom layer containing HPA, water
and fructose. To verify this hypothesis, fructose was added to the
monophasic reaction mixture, and the monophasic solution separated
into two phases (Figure S6, ESI†). The top layer contained GVL and
GBL, the Ru/TiO2 and HPA were reserved in the bottom layer. More
than 96 wt% of formed GVL can be separated in the top layer by
adding 5 g fructose (Table S6, ESI†). The colour of the top layer
become darker and the bottom layer become clear, implying that
soluble humins was enriched in GVL/GBL layer (Figure S6, ESI†).
Meanwhile, to detect the possible leaching of HPA in the top layer,
the content of phosphorus and tungsten in the top layer was analyzed
by ICPꢀOES (Table S7, ESI†). The amount of HPA in the top layer
was gradually reduced by increasing the amount of added fructose.
Particularly, the amount of HPA in the top layer was trace when 5 g
fructose was added. This result implied that the leaching of HPA to
the top layer during the separation process was avoided by adding
proper amount of fructose. After separation, the recycle of combined
HPAꢀRu/TiO2 catalysts was studied (as shown in Figure 1). More
than 60 mol% of GVL yield was achieved after the combined
catalysts were reused for three times.
Generally, inulin is a polysaccharide which will produce fructose
in the acid catalytic process, while sucrose will form equal amount
of glucose and fructose by hydrolysis. Based on the aforementioned
results, it is likely that inulin and sucrose can be effectively
converted to GVL over combined HPA and Ru/TiO2 catalyst. A high
GVL yield of more than 70 mol% was obtained from inulin (Table 4,
entry 1), which was higher than those in literature concerning the
direct conversion of carbohydrates into GVL. Meanwhile, preferable
yields of GVL were acquired with sucrose and glucose as resources
(Table 4, entry 2ꢀ3), which demonstrated the great potential of HPAꢀ
Ru/TiO2 catalysts for transforming glucose to GVL in GBL/water.
Additionally, the hydrolysis of sucrose to LA was studied (Figure S7,
Table 2 The effects of water content and total amount
of GBL/water solvent on GVL yield a
Entry
Solvent
Water
GVL
volume/ml
content/vol%
yield/mol%
1
2
20
20
20
20
20
20
30
15
10
5
5
51.6
56.7
57.3
51.1
48.4
35.1
52.8
60.8
67.6
40.5
10
20
30
40
50
20
20
20
20
3
4
5
6
7
8
9
10
a: 1 g Dꢀfructose, 130 oC, H2, 4 MPa, reaction time 6 h, 0.4
g HPA, 0.2 g 2 wt% Ru/TiO2; no fructose or LA was
detected after the reaction in all experiment runs.
The solution after the reaction was a monophasic mixture
containing mainly water, GBL, GVL, and HPA that has been
dissolved in water, and Ru/TiO2 remained as a solid. If GVL is
efficiently separated from the reaction mixture, the remaining
GBL/water and HPAꢀRu/TiO2 catalysts can be reused for the
conversion of fructose to GVL. Fructose dissolves well in water
whereas it hardly dissolves in GVL at room temperature. This ESI†). The conversion of sucrose was completed within 45 min.
phenomenon suggested to us that the hydroxyls of fructose have a
much tighter coordination with water than GVL. Meanwhile, a
weaker interaction existed between GVL and water compared with
GBL owing to 4ꢀmethyl group in GVL. When fructose is added into
Glucose was detected within 4 h while no fructose was detected in
the reactions. It was demonstrated that the hydrolysis of sucrose and
its degraded fructose was much faster than that of glucose.
Furthermore, maltose and starch were applied as the sources for oneꢀ
This journal is © The Royal Society of Chemistry 2012
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DOI: 10.1039/C5GC00110B
Conclusions
The strong Brønsted acid catalyst HPA combined with a
hydrogenation catalyst of Ru/TiO2 were applied for the oneꢀ
step conversion of carbohydrates (cellulose, inulin, starch,
sucrose, maltose, glucose and fructose) to GVL. The basicity of
solvent greatly influenced the acid strength of HPA, and
thereby affected the catalytic efficiency of HPA. GBL/water
solvent favored the preservation of the strong acidity of HPA
compared with pure water or other water/organic solvents
(methanol, ethanol and 1,4ꢀdioxane), and promoted the catalytic
efficiency of HPA consequently. The efficient conversion of
carbohydrates to GVL can be achieved at mild conditions (130
o
oCꢀ150 C, 4 MPa H2) over combined HPAꢀRu/TiO2 catalysts
in GBL/water (80/20, vol/vol) solvent. Specifically, GVL yields
of 70.5 and 67.6 mol% were obtained for inulin and fructose
respectively, and a yield of 40.5 mol% was acquired for
cellulose. Moreover, a practical method for GVL separation and
catalyst recycling was developed. The monophasic solution
after the reaction separated into two phases with the addition of
fructose. More than 96 wt% of formed GVL can be obtained in
the organic phase, while the aqueous phase that contained water,
GBL and HPAꢀRu/TiO2 catalysts can be reused for the
conversion of sugars into GVL. More than 60 mol% of GVL
yield was obtained over HPAꢀRu/TiO2 catalysts in GBL/water
solvent after three recycling runs, indicating the promising
future of this reaction system for a large scale production of
GVL from carbohydrates.
Figure 1 The recycle of HPA and Ru/TiO2 catalysts. The
conditions in each recycling run: 130 oC, 4 MPa H2 pressure. A
certain amount of fresh HPAꢀRu/TiO2 catalysts, water and GBL were
added to reach an identical reaction condition to the original reaction
(fructose: HPA: Ru/TiO2: water (20 vol%)/GBL solvent=1 g : 0.4 g :
0.2 g : 10 ml) before each recycling run.
step production of GVL. Maltose and starch gave 44.6% and 48.3%
yield of GVL respectively (Table 4, entries 4ꢀ5). In comparison with
fructose, the conversion of glucose to LA is more difficult for the
isomerization glucose to fructose is necessary. This led to the lower
GVL yields from glucose and glucoseꢀderived polysaccharides
(sucrose, maltose and starch) than those from fructose and inulin.
As the most abundant biomass, cellulose is considered as an ideal
resource to produce GVL. However, GVL is presently produced
from cellulose via multiꢀstep method under drastic conditions.19ꢀ21 To
reduce the production cost, a direct conversion of cellulose into GVL
Experimental Section
All experiments were performed in a batch reactor with a
magnetic stirrer. Typically, sugar (1 g) and a certain volume of
solvent were added in the vessel, followed by the addition of
the catalyst Ru/support (0.2 g) and a certain amount of HPA.
Before each run the vessel was sealed and flushed with H2 to
exclude the air for five times. After reactions, the vessel was
cooled down. The reaction products were centrifuged for 10
min and then filtrated to obtain a clear solution. The samples
were analyzed by HPLC (Agilent 1260) with a Shodex SHꢀ
1821 capillary column (300mm×8mm×0.6ꢁm) and a GC
(Agilent 7890) equipped with an ABꢀINNOWAX capillary
column (30 m×0.32 mm×0.5 ꢁm). Standard solutions were used
to obtain the calibration curves to calculate concentrations of
the compounds by the external standard method.
Table 4 Direct conversion of carbohydrates to GVL a
Entry
Substrate
GVL yield%
1
2
3
4
5
6
Inulin
Sucrose
Glucose
Maltose
Starch
70.5
58.5
55.1
44.6
48.3
40.5
Acknowledgements
Cellulose
a: 1 g carbohydrate, H2 4 MPa, 150 oC, reaction time 6 h,
HPA, 0.4 g, 10 ml of 20 vol% water/GBL mixtures; no
LA was detected after the reaction in all experiment runs.
The authors gratefully acknowledge the financial support of the
Major State Basic Research Development Program of China
(973 Program) (no. 2012CB215305).
is desirable but more challenging, for the hydrolysis of cellulose into
glucose is required. The direct conversion of cellulose to GVL was
investigated over combined HPAꢀRu/TiO2 catalysts in GBL/water
Notes and references
a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry,
Chinese Academy of Sciences, Taiyuan 030001, PR China.
E-mail: zhuyulei@sxicc.ac.cn; Fax: +86-351-7560668;
Tel: +86-351-7117097
o
solvent at 150 C and 4 MPa H2 (Table 4, entry 6). Surprisingly, a
preferable yield of 40.5% to GVL was acquired. This result indicated
the excellent ability of HPA in catalyzing the degradation of
cellulose to LA in the water/GBL solvent.
b University of Chinese Academy of Sciences, Beijing, 100049, PR China.
c Synfuels China Co. Ltd., Taiyuan 030032, PR China.
4 | J. Name., 2012, 00, 1-3
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Green Chemistry
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DOI: 10.1039/C5GC00110B
Direct conversion of carbohydrates (cellulose, starch, inulin, maltose, sucrose, glucose and fructose) to
γꢀvalerolactone efficiently facilitated by solvent effect.