Conversion of biomass derived valerolactone into high octane number gasoline with an ionic liquid

Article abstract of DOI:10.1039/c4gc01792g

Conversion of biomass into gasoline of high octane number is challenging. In this study, conversion of biomass-derived γ-valerolactone into gasoline was achieved by decarboxylation of valerolactone to produce butenes and alkylation of the produced butenes with butane using [CF₃CH₂OH₂][CF₃CH₂OBF₃] as an efficient catalyst. The obtained gasoline was rich in trimethylpentane with a high research octane number of 95.4. This journal is

Full text of DOI:10.1039/c4gc01792g

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ARTICLE TYPE
Conversion of Biomass Derived Valerolactone into High Octane Number
Gasoline with Ionic Liquid
Jiayu Xin, Dongxia Yan, Olubunmi Ayodele, Zhan Zhang , Xingmei Lu, Suojiang Zhang*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
Conversion of biomass into gasoline with high octane number 50 Octane Number (RON) or Motor Octane Number (MON). Linear
is challenging. In this study, conversion of biomass-derived γ
valerolactone into gasoline was achieved by decarboxylation
of valerolactone to produce butenes and alkylation of
produced butenes with butane using
CF CH OH ][CF CH OBF ] as an efficient catalyst. The
alkanes always have very low RON and MON. For example, the
RON of nꢀheptane is 0, while that of isooctane (2,2,4ꢀ
trimethylpentane) is 100. Gasoline with a higher octane number is
less prone to autoꢀignition and can withstand a greater rise in
temperature during the compression stroke of an internal
combustion engine without autoꢀigniting, thus allowing more
power to be discharged by higher compression ratio. In order to
meet the requirement of antiknock properties, additives including
MTBE, ETBE, isooctane and toluene tetraethyllead or
-
1
0
5
5
[
3
2
2
3
2
3
obtained gasoline was rich in trimethylpentane with a high
research octane number of 95.4.
Conversion of biomass into hydrocarbons is one of the most
possible alternatives to alleviate the environmental, political, and
economic burdens associating with the depletion and
2
0, 21
60
oxygenated compounds are usually added into gasoline.
1
2
2
3
3
4
4
5
0
5
0
5
0
5
However, these additives have many confirmed or nonꢀconfirmed
drawbacks. The best choice is to produce the gasoline with more
1
, 2
consumption of fossilꢀbased resources. In the past several years,
much effort was devoted to the research on producing
hydrocarbons with extended carbon chains by hydrogenation of
22, 23
C8 alkanes and more branches.
3
ꢀ5
carbohydrate derivatives. One of the earliest efforts was the
6
aqueous phase reforming (APR) process, by which, sugars were
converted to alkanes by hydrogenation with noble metals as
7
catalysts. Later, some important approaches were developed by
8, 9 8, 10
11
12ꢀ14
Dumesic et al.,
Corma et al. and others.
In these
approaches, the indispensable intermediates employed were 5ꢀ
hydroxymethyl furfural and furfural derived from C6 and C5
sugars. The production costs of these intermediates are high due
to high energy consumption in separation and relative low
65
Scheme 1. Production of high octane number gasoline from GVL
15
16
availability. Recently, Dumesic et al. reported an approach
for the production of alkenes by polymerization of butenes from
decarboxylation of γꢀvalerolactone by solid acid catalyst.
However, the products of above processes are alkanes/alkenes
Therefore, we developed a process for the production of
highly branched alkanes rich in trimethylpentane as gasoline with
high octane number. Scheme 1 shows the process for the
production of high octane number gasoline from γꢀvalerolactone
without branch or with single branch, which only can be used as 70 (GVL), which can be produced by hydrogenation of biomassꢀ
1
7
24ꢀ29
30
substitute for diesel fuel or additives of jet fuels. In addition, the
produced fuels contains significant amount of olefin, peticularly
for the fuels produced by dimerization of butenes. In order to
ensure the stability of the fuel, olefin content is strictly required
derived levulinic acid
or directly from fructose. The first
step of the process is decarboxylation of GVL to give butenes
including 1ꢀbutene, transꢀ2ꢀbutene and cisꢀ2ꢀbutene with
SiO /Al O as the catalyst. A part of butenes are hydrogenated
2 2 3
1
8
to be lower than 18%. The research on the production of bioꢀ 75 and isomerized to produce isobutane. Isobutane also can be
31
based alkanes for the purpose of gasoline, the biggest consumed
transportation fuel, is very rare. The main obstacles may be
concluded as: 1) it is difficult to control the carbon numbers of
produced via bioethanol in a high yield. Then, remained butenes
react with isobutane to give isooctane as the gasoline fuel. The
use of acidic ionic liquid [CF
CH OH ][CF CH OBF ] provides
2 2 3 2 3
3
alkanes from 6ꢀ12, especially to control the C content with the
a high yield of highly branched alkanes and thus ensures a high
8
19
32, 33
highest potion; 2) it is difficult to control the antiknock index to 80 octane number of the products.
satisfy the requirement of gasoline motors.
The carbon numbers of alkanes is crucial for the density,
fluidity, viscosity, ignition, distillation and vapor pressure
parameters of gasoline, while antiknock index indicates the
resistance to autoignition. As one of the most important fuel
properties of gasoline, antiknock index is indicated by Research
Experimental
Catalyst preparation
85
Preparation of SiO /Al O
3
2
2
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[journal], [year], [vol], 00–00 | 1

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DOI: 10.1039/C4GC01792G
SiO /Al O solid catalyst was prepared by a sol–gel method. A
temperature program for GC analysis were: initial column
2
2
3
o
o
o
o
known amount Si(OC H ) (99%, Xilong Chemical Industry) was
temperature 40 C, hold for 10 min, 0.5 C/min to 80 C, then 5 C
2
5 4
o
dissolved in ethanol, and its pH value was adjusted at 3.0 by
/min to 300 C hold for 15 min.
o
glacial acetic acid. The solution was maintained at 50 C under
65
5
0
5
0
5
0
5
0
5
0
5
0
vigorous stirring to obtain a homogenous silica sol. A known
mount of aluminum precursor Al(NO ) ·9H O (99%, Xilong
Results and discussion
3
3
2
Conversion of GVL into butenes
Chemical Industry) was dissolved in distilled water. Si(OC H )
2
5 4
and Al(NO ) ·9H O solutions were then mixed and stirred for 2 h
3
3
2
The products of decarboxylation of GVL was a mixture of
butenes including 1ꢀbutene, 2ꢀbutene (cisꢀ2ꢀbutene and transꢀ2ꢀ
o
at 50 C. Ammonium hydroxide solution (NH OH, Sigma–
4
1
1
2
2
3
3
4
4
5
5
6
Aldrich) was slowly added into the mixed solution to form a
7
7
8
0
5
0
butene) and CO . For a reaction time of 4 h, low temperature
2
o
hydrogel at pH of 8.0, after aged for 24 h at 25 C, the liquid was
gave a low yield (Table 1). A good yield of 97 % was achieved at
removed by filtration. The remained solid was washed with
distilled water for several times to remove ammonium nitrate and
subsequently washed with ethanol to form porous structure of
hydrogel. The resulted gel was dried in a convection oven at
o
a temperature of 350 C (entry 3, Table 1). However, a
o
temperature higher than 350 C decreased the yield of butenes
possibility due to the coke formation, likely by polymerization of
pentenoic acid produced by ring open reaction of GVL, which
further decreased the activity of SiO /Al O catalyst. The side
reactions were also noticed at high temperature, some cracking
products including methane and propane were found at 400 C.
Reaction time also affected the yields of butenes, 1 h reaction
only gave a yield of 50 %, while increases the reaction time to 4 h
increased the yield to 97 % and further prolonged the reaction
time longer than 4 h had minimal effect on the decarboxylation
(Table 1).
34
o
o
1
00 C for 24 h, and then calcinated at 500 C for 4 h to get
2
2
3
SiO /Al O catalyst.
2
2
3
o
Preparation of [CF CH OH ][CF CH OBF ]
3
2
2
3
2
3
1
00 g 2,2,2ꢀtrifluorothanol (CF CH OH, 99%, J&K Scientific
3 2
Ltd.) was placed in a 500 ml polytetrafluoroethylene bottle with a
rubber cap, an inlet and a safety outlet. BF (99%, Heli Chemical
3
Industry Co.) contained in a high pressure steel cylinder was
slowly released to the bottle through a 3 mm diameter
polytetrafluoroethylene tube. In order to remove the heat
generated during the reaction, the bottle was surrounded by dry
ice and the reactants were stirred continuously. The weight of the
8
5
Table 1. GVL conversion and butane yield under different reaction
condition with 10% SiO
2
/Al
2
O
3
as the catalyst in batch type reactor
bottle with reactants was recorded periodically. BF was stopped
3
a
o
Yield of butene (mol%)
to pass when no weight increase was observed, which means the
reaction between BF and CF CH OH was finished. The obtained
Entry
Time (h)
Temp.( C)
1
ꢀbutene
2ꢀbutene
Total
7
3
3
2
1
2
3
4
5
6
7
8
4
4
4
4
1
2
6
10
250
300
350
400
350
350
350
350
2
5
product was found to be [CF CH OH ][CF CH OBF ].
18
39
33
19
33
37
36
41
58
57
41
54
60
61
59
97
90
50
87
97
97
3
2
2
3
2
3
Experimental procedure
Decarboxylation
a
Decarboxylation of GVL (2 g, 99%, purchased from J&K
Scientific Ltd.) was carried out in a 50 ml batchꢀtype reactor with
moles of actual butene/moles of theoretic butene
o
continuous stirring from 250ꢀ350 C with 10% SiO /Al O
2
2
3
9
0
Preparation of high octane number gasoline
catalyst mentioned above.
Alkylation
CO2 produced can be easily separated from butenes by
increasing the pressure above ambient pressure to liquefy
35
butenes. The remained butenes can be hydrogenated and
Alkylation of isobutane and butenes (1ꢀbutene: 2ꢀbutene=3:7,
supplied by Changlin Senmao Chemical Ltd Co., >99.9 % purity)
was performed in a 100 ml stirred stainless steel reactor. Reaction
temperature was maintained by placing the reactor in a cooling
bath filled with cycling ethanol. Even though, a temperature
isomerized to produce isobutane, which were also extensively
36ꢀ40
9
5
studied and reported.
Some proving experiments were carried
and supported in ESI. In this study, Pd/C was used and almost
completely conversions and near 100% yields were achieved at
relatively mild conditions (Table S2). By using Pd/ZSMꢀ8, nꢀ
butane was also isomerized to isobutane with a moderate yield
o
increase of 3ꢀ8 C inside of the reactor was observed.
[
CF CH OH ][CF CH OBF ] catalyst was firstly placed in the
3 2 2 3 2 3
100 (Table S3).
The production of gasolineꢀranged alkanes from butenes and
reactor and then the isobutane and butane mixture was pumped
into the reactor by a syringe pump to carry out the reaction.
isobutane can be performed by alkylation catalyzed by superacid
catalyst. BF is a widely used Lewis acid catalyst for high acidity
3
Analytical method
catalytic reactions directly or by supported on mesoporous
05 materials. It also can form coordination of compositions 1:1 or
1
The gas and liquid products were analyzed by a GC (Agilent
GC 7890) equipped with a flame ionization detector and a DBꢀ
Petro column (0.25 mm*100 m, Agilent Co.). The analysis
conditions were: nitrogen as carrier gas, split ratio=26:1, injector
1
:2 with organic compounds containing oxygen atoms.
Commonly available adduct, BF ·2Ethanol is a conveniently
3
handled liquid and has catalytic effects for many organic reaction.
But these adducts cannot be used for alkylation reaction due to
10 high solubility of ethanol in produced alkanes. In our study, it
o
o
temperature=250 C, detector temperature=300 C. The
1
2
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DOI: 10.1039/C4GC01792G
was found that if the hydrogen atoms of methyl group are
replaced by fluorin, its solubility in alkanes is neglectable (≈
We carried out the alkylation reaction of butenes (1ꢀbutene:2ꢀ
butene=3:7) and isobutane (butenes:isobutane=1:10) at 10 C to
o
0
.5 %). We considered liquefying BF with CF CH OH to form
produce saturated hydrocarbons. As expected, the high octane
number gasoline was produced in complete conversion of butenes.
The effect of reaction time can be elucidated by the changes in
3
3
2
an ionic liquid as a good catalyst for alkylation reaction of
isobutane and butenes produced from GVL.
1
5
5
41
the product distributions and calculated RON. Figure 1 shows
the effect of reaction time on the alkylation of isobutane with
butenes catalyzed by [CF CH OH ][CF CH OBF ] at various
3
2
2
3
2
3
o
20
temperatures. At 0 C, a higher C8 fraction and octane number
were achieved with a reaction time of 5 min. However, the
highest C8 fraction and octane number were achieved at 10 C,
indicating the most suitable reaction temperature was 10 C. At
10 C, the highest RON increased from 5 to 10 min and decreased
A
100
Co nv er s io
1
n
00
o
8
0
0
0
0
0
9
9
5
o
o
6
4
2
T
MP
0
25 from 10 to 30 min, the highest RON was obtained at a reaction
time of 10 min. Meanwhile, the most valuable C8 fraction also
showed the same trend. A reaction time longer than 10 min
leaded to the decreases of the RON and C9 content (Figure 1A).
The decrease is due to the oligomerization reactions responsible
C8
RNO
MON
C9+
85
80
C5-C7
D
MH
5
10
15
20
25
30
35
30
for higher C9+ fractions with longer reaction time. For all
Reaction time (min)
o
reaction times at 10 C, more than half of alkanes obtained were
B
1
00
Co nv er s io
1
n
00
C8 fractions. Under optimum condition, more than 80% alkanes
1
6
obtained was C8 fraction. In the pioneer work of Dumesic et al,
the highest C8 fraction produced by dimerization of butenes was
80
60
40
20
0
9
9
8
5
C8
C9+
35 only 43%, which was greatly lower than the result here. The main
products obtained in their study are olefins, as unsaturated
hydrocarbons, they have relative lower stability and strong
tendencies to react with butene to form higher molecular olefins
including C 12 and C16. Furthermore, the products from our
T
MP
RON
0
MON
5
C5-C7
D
MH
40
approach are saturated hydrocarbons having better stability at
80
5
10
15
20
25
30
35
lower reaction temperature. Although the C8 fraction is the most
Reaction time (min)
42, 43
suitable components for gasoline fuel,
the trimethypentanes
C
Co nv er s io
n
100
100
(TMPs) are the most favored ones because TMPs have an octane
number of 100 while that of dimethylhexanes (DMH) is 44. It is
seen that the highest C8 and TMP selectivities, lowest DMH and
C9+ fraction were obtained at a reaction time of 10 min, which
ensured the highest TMP contents and corresponding highest
RON and MON, while prolonged the reaction time decreased the
C8 content. The highest RON of 95.4 of the products was
50 achieved at the optimum conditions without any additives. When
the reaction time was increased to 30 min, the C9+ fraction also
increased greatly from 23% to 57% possibly because
oligomerization reactions predominated under these conditions.
80
60
40
20
0
45
C8
95
RON
T
MP
MON
90
C9+
85
C5-C7
D
MH
80
5
10
15
20
25
30
35
Reaction time (min)
D
100
Co nv er s io
n
100
Effect of reaction temperature on the reaction catalyzed with
5
6
6
5
0
5
[CF CH OH ][CF CH OBF ] and with a reaction time of 10 min
3 2 2 3 2 3
8
6
4
2
0
0
0
0
0
9
9
8
5
is shown in Figure 2. It is seen that both valuable TMP and C8
C8
o
fractions achieved high values at 10 C, while the increase of the
T
MP
o
RON
MON
0
temperature to 20 and 30 C lowered the TMP content. For all
temperatures, complete conversions of butenes were achieved. At
C9+
o
temperatures higher than 10 C, the increases of C9+ and C5ꢀC7
5
C5-C7
fractions became significant. Considering the decrease of C8
fraction, it is certain that some produced C8 hydrocarbons added
to isobutylene to form higher homologues, a part of which further
cleaved to lower molecular alkanes including C5, C6 and C7 at
higher temperature.
D
MH
80
5
10
15
20
25
30
35
Reaction time (min)
Figure 1. Effect of reaction time on the alkylation of isobutane and
butenes catalyzed by [CF
o
3
CH
2
OHo
2
][CF
3
CH
2
3
oOBF ] at (A) 0 C; (B) 10
o
1
0
C; (C) 20 C; (D) 30 C
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DOI: 10.1039/C4GC01792G
Table 3. Key properties of produced gasoline and the specifications of EN
18
2
28
100
Co nv er s oi n
100
Properties
Requirements
95
Gasoline
95.4
Test methods
8
0
9
5
Research octane
number (RON)
Lead content
[mg/kg]
Sulfur content
[mg/kg]
44
>
Ref.
8
60
5
Not detected
Not detected
748
EN 237
R NO 90
T MP
40
MNO
5
0
EN ISO 3675
EN ISO
C9+
85
3
Density [kg/m ]
720ꢀ775
20
D MH
2
0846
C5-C7
Clear and
bright
Clear and
bright
Visual
inspection
ASTM D
1319
ASTM D
1319
Appearance
0
80
0
10
20
30
o
Olefins [% (V/V)]
Aromatics [%
<18
0.5
Not detected
Not detected
0
Reaction temperature ( C)
3
5
(
V/V)]
Benzene content [%
V/V)]
Oxygen content [%
m/m)]
Figure 2. Effect of reaction temperature on the alkylation of
isobutane and butenes catalyzed by [CF
3
CH
2
OH
2
][CF
3
CH
2
OBF
3
]
1
EN 238
(
with a reaction time of 10 min
<
2.7
EN 1601
(
5
a
3 2 2 3 2 3
Table 2. Reusability of [CF CH OH ][CF CH OBF ]
30
Since the products produced by this method should be
acceptable for transportation fuel, the properties were determined
and the requirements were shown in Table 3. From Table 3, it is
Exp. Cycles
C5 [%]
C6 [%]
1
1
2
3
1
2
3
5
2
3
4
7
9
1
3
3
11
1
2
2
3
4
1
8
seen that key properties can meet the specifications of EN 228.
C7 [%]
2
3
Some values, lead, sulfur, olefins, aromatics, benzene contents
are better than the requirement. Especially, the RON can also
meet the specification without adding any additives commonly
used in petroleumꢀbased gasoline.
C8 [%]
82
73
9
8
13
95.4
73
64
9
7
20
93.5
63
54
9
6
28
91.6
50
41
9
5
42
46
39
7
6
47
41
35
5
7
54
88.0
35
TMP [%]
DMH [%]
TMP/DMH
C9+ [%]
RON
88.9
88.8
a
Reaction conditions: 50 ml butenes and isobutane (1:10), 30 ml
Elucidation of the activity of [CF CH OH ][CF CH OBF ]
3
2
2
3
2
3
o
[CF
3
CH
2
OH
2
3
][CF CH
2 3
OBF ], 10 min, 10 C. Full table is available in Table
40
S4.
10
15
20
25
The reusability and regeneration of the ionic liquid catalyst are
important factors for the application. The reusability of
[
CF CH OH ][CF CH OBF ]
on
product
distribution,
3
2
2
3
2
3
TMP/DMH, RON were examined with isobutane/(1ꢀbutene+2ꢀ
o
butene) of 10, reaction time of 10 min at 10 C. The
Scheme 2. Formation of [CF
3
CH
2
OH
2
][CF
3
CH
2
3
OBF ] and its acidity
isobutane/butenes mixtures reacted in the reactor with catalyst
and then the reactant/product phase was removed by phase
separation. Fresh reactants were then added for the next
experimental cycle. Totally 12 cycles were examined. From
Table 2, it is shown that the catalyst showed similar performance
in the first 6 reactions, noticeable changes in product quality with
higher ratio of C9+ fraction were observed in the following
reactions, which also caused the gradual decrease of RON. This is
most likely due to the acidity decrease by separation of catalyst
with reactant/product phases. If the catalyst is used in the
continuous process, it may show better performance.
[
CF CH OH ][CF CH OBF ]
showed
a
very
good
3
2
2
3
2
3
4
5
5
5
0
5
performance for the conversion of bioꢀbased butenes and
isobutane into high octane number gasoline. After completely
saturated CF CH OH with BF , it was found the obtained
3
2
3
complex
has
a
molecular
formula
of
1
[
CF CH OH ][CF CH OBF ]. Figure 3 shows the H NMR of
3 2 2 3 2 3
CF CH OH and [CF CH OH ][CF CH OBF ]. CH proton can
3
2
3
2
2
3
2
3
2
be easily assigned to around 4.1 ppm and OH proton assigned to
.4 ppm without BF . After saturated with BF , the chemical shift
5
3
3
of hydroxyl in CF CH OH of 5.4 ppm shifted to 8.8 ppm due to
3
2
the high electron withdrawing ability of BF . BF may form a
bond with oxygen atom of CF CH OH and lead to complete
3
3
3
2
transfer of the proton to CF CH OH as following equilibrium
3
2
+
ꢀ
(
Scheme 2) to form [CF CH OH ] cation and [CF CH OBF ]
3 2 2 3 2 3
anion as shown in Scheme 2. From this, it can be proposed that
adduct of BF and CF CH OH is ionic liquids in its nature.
3
3
2
4
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3
3
4
4
0
5
0
5
However, a variety of side reactions that leads to produce low
octane number hydrocarbons depending on the reaction
conditions. The iꢀC8+ cation can undergo isomerization catalyzed
by acid catalyst through rearrangements giving various isomeric
cations leading to the formation of low octane isomers such as
DMH . The iꢀC8+ cation also can add to isobutylene to form
higher homologues such as iꢀC12+, iꢀC16+, etc. These cations
lead to the formation of heavier alkanes or alkenes. The larger
isomeric carbocations also can cleave into smaller carbocations
36
(C5+, C6+, and C7+) and alkenes through βꢀscission, which can
be considered as the reverse process of the addition of
45
carbocations to alkenes . For example, iꢀC12+ may cleave into
+
+
+
C H + C H
or C H + C H
or C H + C H . The
7 14 5 11
5
10
7
15
6
12
6
13
produced smaller carbocations abstracts hydride from isobutane
+
forming the iꢀC4 cation and corresponding hydrocarbons having
lower octane numbers compared with 2,2,4ꢀTMP.
Conclusions
In summary, we describe here a method that a practical
feedstock (GVL) is efficiently converted to high octane number
gasoline rich in TMP via decarboxylation and alkylation reactions.
Decarboxylation of GVL produces butenes including 1ꢀbutene,
transꢀ2ꢀbutene and cisꢀ2ꢀbutene in the highest yield of 97% with
SiO /Al O . After hydrogenation and isomerizaiton of a part
1
3 2 3 2 2 3 2 3
Figure 3. H NMR of CF CH OH and [CF CH OH ][CF CH OBF ]
50
41
5
Olah et al. found that the most suitable acid strength for
alkylation was about H =−10.7. An acid strength too high (H <ꢀ
4.1) leads to produce cracked products, while too low favors
0
0
1
2
2
3
butenes to isobutane, high octane number gasoline can be
produced by alkylation between butenes and isobutane with
[CF CH OH ][CF CH OBF ] as the catalyst. The products are
mixture of alkanes rich in TMPs, which has a RON of 100 and
serve as the most suitable component for high octane gasoline.
The highest octane number of the product is 95.4, indicating that
60 high quality gasoline can be produced from biomass derived
oxygenated compounds without hydrodeoxygenation and without
any additives.
oligomerization reaction. The result obtained from this study
indicats that [CF CH OH ][CF CH OBF ] is high acidic
contributing by [CF CH OH ] . The reaction catalyzed by H
3 2 2
55
3
2
2
3
2
3
+
+
3
2
2
3
2
3
1
1
2
0
5
0
provided by [CF CH OH ][CF CH OBF ] is mechanistically
3
2
2
3
2
3
considered as a chain process as shown by Scheme 3. Butene
+
+
reacts with H to form iꢀC cation, which further reacts with
4
+
butane and forms iꢀC8 cation as the intermediate. In the presence
of isobatane, its hydride is abstracted by iꢀC cation and forms iꢀ
C4 cation, which keeps the catalytic cycle going. The objective
+
8
+
product from this reaction, 2,2,3ꢀtrimethylpentane (2,2,3ꢀTMP),
which has a research octane number of 100, is the most suitable
Notes and references
component for high octane gasoline. At the same time,
This work was supported by National Basic Research Program of China
isomerization of iꢀC8 cation also proceeds and further reacts with 65 (2013CB733506), National Natural Science Foundation of China (No.
+
isobatane to produce 2,2,4ꢀTMP, 2,2,3ꢀTMP and 2,3,4ꢀTMP.
Conversion of 1ꢀbutene is also proceeds via similar reactions.
21210006, 21276260), International S&T Cooperation Program of China
(2014DFA61670), External Cooperation Program of BIC, Chinese
Academy of Sciences (GJHZ201306) and Key Project of Natural Science
Foundation of Beijing of China (No. 2131005).
CH
3
7
7
0
5
3
H C HC
CH
3
Beijing Key Laboratory of Ionic Liquids Clean Process, State Key
Laboratory of Multiphase Complex System
Institute of Process Engineering, Chinese Academy of Sciences
Zhongguancun, Beiertiao, Haidian, Beijing 100190 (China)
Fax: (+86) 10-8262-7080
H+
CH3
+
+ nC H
4 10
+CH
H2
C
C
H
3
C
CH
CH CH
3
H
3
C
CH
2
CH
3
CH
3
CH
3
CH
3
C+
+CH CH
E-mail: sjzhang@ipe.ac.cn
H
2
C
+
H
3
C
CH
CH CH
3
H
3
C
C
2
CH
3
CH
3
CH
3
CH
3
†
Electronic Supplementary Information (ESI) available: Experimental,
CH
3
supported tables and figures. See DOI: 10.1039/b000000x/
CH
3
H
3
C
HC
80
CH
3
CH
3
CH
3
H
3
C
C
+CH CH
CH
2
CH
3
C+
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| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C4GC01792G
Biomassꢀderived γꢀvalerolactone was converted into high octane number gasoline with
SiO /Al and [CF CH OH ][CF CH OꢀBF ] as efficient catalysts.
2
2
O
3
3
2
2
3
2
3