Direct Synthesis of Renewable Dodecanol and Dodecane with Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems

Article abstract of DOI:10.1002/cssc.201601563

For the first time, we demonstrated two integrated processes for the direct synthesis of dodecanol or 2,4,8-trimethylnonane (a jet fuel range C₁₂-branched alkane) using methyl isobutyl ketone (MIBK) that can be derived from lignocellulose. The reactions were carried out in dual-bed continuous flow reactors. In the first bed, MIBK was selectively converted to a mixture of C₁₂ alcohol and ketone. Over the Pd-modified magnesium– aluminium hydrotalcite (Pd-MgAl-HT) catalyst, a high total carbon yield (73.0 %) of C₁₂ oxygenates can be achieved under mild conditions. In the second bed, the C₁₂ oxygenates generated in the first bed were hydrogenated to dodecanol over a Ru/C catalyst or hydrodeoxygenated to 2,4,8-trimethylnonane over a Cu/SiO₂ catalyst. The as-obtained dodecanol can be used as feedstock in the production of sodium dodecylsulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), which are widely used as surfactants or detergents. The asobtained 2,4,8-trimethylnonane can be blended into conventional jet fuel without hydroisomerization.

Full text of DOI:10.1002/cssc.201601563

Accepted Article
Title: Direct Synthesis of Renewable Dodecanol and Dodecane with
Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems
Authors: Xueru Sheng, Ning Li, Guangyi Li, Wentao Wang, Aiqin
Wang, Yu Cong, Xiaodong Wang, and Tao Zhang
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To be cited as: ChemSusChem 10.1002/cssc.201601563
Link to VoR: http://dx.doi.org/10.1002/cssc.201601563
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10.1002/cssc.201601563
ChemSusChem
COMMUNICATION
Direct Synthesis of Renewable Dodecanol and Dodecane with
Methyl Isobutyl Ketone over Dual-Bed Catalyst Systems
Xueru Sheng,[a,b] Ning Li,*[a,c] Guangyi Li,[a] Wentao Wang,[a] Aiqin Wang,[a,c] Yu Cong,[a] Xiaodong
Wang[a] and Tao Zhang*[a,c]
Abstract: For the first time, we demonstrated two integrated
processes for the direct synthesis of dodecanol or 2,4,8-
trimethylnonane (a jet fuel range C12 branched alkane) with methyl
isobutyl ketone (MIBK) which can be derived from lignocellulose.
The reactions were carried out in two-bed continuous flow reactors.
In the first bed, MIBK was selectively converted to a mixture of C12
alcohol and ketone. Over the Pd modified magnesium-aluminium
hydrotalcite (Pd-MgAl-HT) catalyst, high total carbon yield (73.0%) of
C12 oxygenates can be achieved under mild conditions. In the
second bed, the C12 oxygenates generated in the first bed was
hydrogenated to dodecanol over the Ru/C catalyst or
hydrodeoxygenated to 2,4,8-trimethylnonane over the Cu/SiO2
catalyst. The dodecanol as obtained can be used as the feedstocks
in the production of sodium dodecylsulphate (SDS) and sodium
dodecyl benzene sulfonate (SDBS) which are widely used as
surfactants or detergents. The 2,4,8-trimethylnonane as obtained
can be blended into conventional jet fuel without hydroisomerization.
intermediate in the production of sodium dodecylsulphate
(SDS)[8] or sodium dodecyl benzene sulfonate (SDBS)[9] which
are widely used as surfactants or detergents. Jet fuel is one of
the most often used transportation liquid fuels. To the best of our
knowledge, there is no report about the direct production of
renewable dodecanol or jet fuel range hydrocarbon using MIBK
as the feedstock. In this work, it was reported for the first time
that dodecanol and 2,4,8-trimethylnonane (a jet fuel range C12
branched alkane) can be directly synthesized in high carbon
yields (~70%) by the reaction of MIBK and hydrogen over dual-
bed catalyst systems. In the first bed, MIBK was selectively
converted to a mixture of C12 alcohol and ketone over the Pd-
MgAl-HT catalyst. In the second bed, the C12 oxygenates
generated from the first-bed was either hydrogenated to
dodecanol over the Ru/C catalyst or hydrodeoxygenated to
2,4,8-trimethylnonane over the Cu/SiO2 catalyst. The strategy for
the two processes was illustrated in Scheme 1.
With the decline of fossil energy and the increase of social
concern about environmental problems, the catalytic conversion
of renewable and inedible biomass to fuels[1] and chemicals[2]
has become a very hot research topic. Lignocellulose is the
major component of the agriculture wastes and forest residues.
Compared with other forms of biomass, lignocellulose is much
cheaper and more abundant. In the recent years, the
substitution of petroleum with lignocellulose-derived platform
molecules as the feedstocks in the production of liquid fuels[3]
and bulk chemicals[4] has drawn tremendous attention.
Acetone is a by-product in the manufacture of bio-butanol and
bio-ethanol by the acetone-butanol-ethanol (ABE) fermentation
of lignocellulose. In a typical ABE fermentation process, butanol,
acetone and ethanol are produced at a weight ratio of 6:3:1.[5]
With the large scale utilization of bio-butanol and bio-ethanol as
the substitute of gasoline, the exploration of big outlets for
acetone is attracting more and more attention.[6] Methyl isobutyl
ketone (MIBK) is a important chemical which has been produced
in industrial scale by the one-step self-aldol condensation/
selective hydrogenation of acetone.[7] Dodecanol is an
Scheme 1. Strategy for the direct production of dodecanol and 2,4,8-
trimethylnonane with MIBK and hydrogen over dual-bed catalyst systems.
In the first part of this work, we investigated the reaction of
MIBK and hydrogen over magnesium-aluminium hydrotalcite
(MgAl-HT) and a series of noble metal modified magnesium-
aluminium hydrotalcite (M-MgAl-HT, M = Pd, Ir, Pt, Ru) catalysts.
The tests were carried out by a fixed-bed continuous flow
reactor (illustrated in Figure S1 of the supporting information) at
553 K and 0.6 MPa H2. To facilitate the comparison, the atom
ratios of M/Al in the M-MgAl-HT catalysts were fixed as 0.02:1.
According to the analysis results of GC-MS (illustrated in
Figures S2-S4 of the supporting information), 2,6,8-
trimethylnon-5-en-4-one (i.e. the compound 1 in Scheme 2)
from the self-condensation of MIBK and some unknown heavy
compounds were detected as the products over the MgAl-HT
catalyst. In contrast, 2,6,8-trimethyl-4-nonanone and 2,6,8-
trimethyl-4-nonanol (i.e. compound 2 and 3 in Schemes 1 and
2) were identified as the two major products from the self-
condensation/hydrogenation of MIBK over the M-MgAl-HT
catalysts. Besides the compounds 2 and 3, methyl-isobutyl
carbinol (MIBC) was also detected in the product. This
compound was generated by the hydrogenation of MIBK over
the M-MgAl-HT catalysts. It is worthy mention that compound 1
[a]
Dr. X. Sheng, Prof. N. Li, Prof. G. Li, Prof. W. Wang, Prof. A. Wang,
Prof. Y. Cong, Prof. X. Wang, Prof. T. Zhang
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
E-mail: lining@dicp.ac.cn; taozhang@dicp.ac.cn
Dr. X. Sheng
University of Chinese Academy of Sciences
Beijing 10049, China
Prof. N. Li, Prof. A. Wang, Prof. T. Zhang
iChEM (Collaborative Innovation Center of Chemistry for Energy
Materials)
[b]
[c]
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Dalian 116023, China
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601563
ChemSusChem
COMMUNICATION
or 2,6,8-trimethylnon-5-en-4-ol (i.e. the compound 4 in Scheme
2), from the hydrogenation of C=O bond in compound 1 was not
detected in the products over the M-MgAl-HT catalysts. This
result can be rationalized because the hydrogenation of C=C
bond in compound 1 is very fast and thermodynamicly more
favorable than the hydrogenation of C=O bond.[10]
(3.8%) were achieved over the Pd-MgAl-HT under nitrogen
atmosphere. These values are even lower than those obtained
over MgAl-HT under the same reaction conditions. Based on
these results, we can see that the hydrogenation of compound 1
is favorable for the production of compound 2 and 3. This result
can be expalined by two reason: As we know, the aldol
condenation is
a
reversible reaction. Therefore, the
hydrogenation of compound 1 from the self-aldol condensation
of MIBK can decrease its concentration in the reaction system
which is benefical for the generation of C12 oxygenates from the
pointview
of
reaction
equilibrium.
Furthermore,
the
hydrogenation of compound 1 can also restrain the retro-aldol
condensation, which may be another reason for the promotion
effect of noble metals. From Figure 1, it was also noticed that
the carbon yield of unexpected MIBC (8.8%) over the Pd-MgAl-
HT catalyst was evidently lower than those over the other M-
MgAl-HT catalysts (>20%), which may be one reason for the
excellent performance of the Pd-MgAl-HT catalyst. According to
literature,[11] the Pd catalyst is highly selective for the
hydrogenation of C=C bond (instead of C=O bond) especially
when it is loaded on basic supports. As we know, the
hydrogenation of C=O bond in MIBK molecule will decrease its
concentration in the reaction system, which is unfavorable for
the self-aldol condensation of MIBK (or the generation of
compound 2 and 3) from the pointview of reaction equilibrium.
The effects of Pd content, hydrogen pressure and reaction
temperature on the catalytic performance of Pd–MgAl-HT were
also studied. As we can see from Figures S6 in supporting
information, the activity of Pd–MgAl-HT catalyst increases with
the increment of Pd content, reaches the maximum when the
atomic ratio of Pd/Al is about 0.02, and decreases with the
further increment of the Pd/Al atomic ratio in Pd–MgAl-HT
catalyst. Analogously, we also noticed that there is also an
optimal hydrogen pressure (or reaction temperature) for the total
carbon yield of C12 oxygenates over the Pd0.02-MgAl-HT catalyst,
respectively. According to the results shown in Figures S7 and
S8, the highest total carbon yield of C12 oxygenates (73.0%) was
achieved over the Pd0.02-MgAl-HT catalyst when the reaction
was conducted at 553 K and 0.6 MPa H2.
Scheme 2. Reaction pathways for the generation of MIBC, compounds 1, 2
and 3 from the reaction of MIBK and hydrogen over the MgAl-HT and M-MgAl-
HT catalysts.
100
80
60
40
20
0
T
T
-H
T
T
T
-H
-H
l
-H
l
-H
l
l
A
l
A
A
A
A
Mg
-Mg
-Mg
2
-Mg
-Mg
2
2
2
.0
.0
.0
Ir 0
.0
0
0
Pt 0
Pd
Ru
Figure 1. MIBK conversion (black bar) and carbon yields of compound 1
(green bar), compound 2 (red bar), compound 3 (blue bar) and MIBC (white
bar) over the MgAl-HT and M-MgAl-HT (M = Pd, Ir, Pt, Ru) catalysts. Reaction
conditions: 1.0 g catalyst, 523 K, 0.60 MPa H2, hydrogen flow rate: 150 mL
min−1, MIBK flow rate: 0.05 mL min−1
.
From Figure 1, we can see that the MgAl-HT catalyst has low
activity and selectivity for the production of C12 oxygenates from
the condensation of MIBK. Over it, 47.0% MIBK conversion and
5.2% carbon yield of compound 1 was achieved at 523 K. After
being modified with small amount of noble metals (Pd, Ir, Pt or
Ru), the MIBK conversion and carbon yields of C12 oxygenates
(i.e. compounds 2 and 3) over the MgAl-HT catalyst were
significantly improved. Among the investigated M-MgAl-HT
catalysts, Pd-MgAl-HT exhibited the highest activity and
selectivity for the conversion of MIBK to compound 2 and 3 (see
Figure 1). Over it, high MIBK conversion (90.6%) and good total
carbon yield (72.0%) of compound 2 and 3 were achieved at
523 K and 0.6 MPa H2. To figure out the promotion effect of
noble metals on the condensation of MIBK over the MgAl-HT
catalyst, we also studied the activity of Pd-MgAl-HT for the self-
condensation of MIBK under nitrogen atmosphere. To faciliate
the comparsion, the experiment was carried under the same
reaction conditions as we used under hydrogen atomosphere.
As we can see from Figure S5 in supporting information, low
MIBK conversion (18.7%) and carbon yields of compound 1
100
80
60
40
20
0
Mesityl oxide
MIBC
2-Pentaneone
2-Heptaneone
Figure 2. Conversion of feedstock (black bar) and carbon yields of ketone
dimer (red bar) and alcohol dimer (blue bar) over the Pd0.02-MgAl-HT catalyst.
Reaction conditions: 1.0 g catalyst, 553 K, 0.60 MPa H2, hydrogen flow rate:
150 mL min−1, ketone (or MIBC) flow rate: 0.05 mL min−1
.
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10.1002/cssc.201601563
ChemSusChem
COMMUNICATION
Subsequently, we also explored the applicability of Pd–MgAl-
HT for the self-condensation of other ketones which can be
derived from lignocellulose. Among them, mesityl oxide can be
produced from the self-aldol condensation of acetone.[12] The 2-
pentanone and 2-heptanone can be obtained by alkylation
reaction of the acetone and ethanol (or butanol).[3f, 13] Moreover,
2-pentanone can also be obtained a by-product in the selective
hydrogenation of furfural to 2-methylfuran,[14] a feedstock in the
production of diesel and jet fuel range branched alkanes.[15]
According to Figure 3, the Pd–MgAl-HT is active for the
used as feedstock in the production of sodium dodecyl benzene
sulfonate (SDBS).[9] The by-product MIBC can be recycled and
used as feedstock to increase the carbon yield of dodecanol.
80
60
Carbon yield of 2,4,8-trimethylnonane
Carbon yield of 2-methylpentane
40
condensation of all the investigated ketones. Over the Pd0.02
-
MgAl-HT catalyst, high carbon yields of C10-C14 oxygenates
(59.7-76.2%) were obtained under the same reaction conditions
as we used for MIBK. Compare with MIBK, slightly lower carbon
yield of C12 oxygenates (68.5% vs. 73.0%) was obtained when
we used mesityl oxide as the feedstock. This can be explained
because mesityl oxide is less reactive than MIBK (due to its
conjugated structure). As the result, mesityl oxide must be
hydrogenated to MIBK then form C12 oxygenates by self-aldol
condensation. It is very interesting that high carbon yield of C12
oxygenates was achieved when we used MIBC as the feedstock.
Compared with MIBK, MIBC is less reactive. This can be
comprehended because MIBC must be dehydrogenated to
MIBK before it is converted to compounds 2 and 3.
20
0
2
5
8
11
14
17
20
23
Time on stream / h
Figure 4. Carbon yields of 2,4,8-trimethylnonane (▲) and 2-methylpentane
(▼) from the reaction of MIBK and hydrogen over the dual-bed catalyst
system of Pd0.02-MgAl-HT and 5wt.%Cu/SiO2. Reaction conditions: 553 K, 0.60
MPa H2; 1.0 g Pd0.02-MgAl-HT catalyst, 1.5 g 5wt.%Cu/SiO2 catalyst, hydrogen
flow rate: 150 mL min−1, MIBK flow rate: 0.05 mL min−1
.
As another option, the C12 oxygenates generated in the first
bed can also be hydrodeoxygenated to 2,4,8-trimethylnonane
and 2-methylpentane when 5wt.% Cu/SiO2 was used as the
catalyst in the second bed (see Figures S9-S11 in supporting
information). High carbon yield (~70%) of 2,4,8-trimethylnonane
was achieved over such a dual-bed catalyst system. The 2,4,8-
trimethylnonane as obtained has the carbon chain length of jet
fuel range and branched chemical structure. As a potential
apllication, it can be blended into conventional jet fuel without
hydroisomerization. The 2-methylpentane which is obtained as
the by-product from this dual-bed catalyst system can be used
as renewable gasoline.
The stabilities of both dual bed catalyst systems were studied.
During the 24 h continuous tests, no evident deactivation was
observed, which means the catalysts are stable under the
investigated conditions. In the future research, it is also possible
to synthesize renewable dodecanol and jet fuel range alkanes
with hexanol or butanol which can be selectively obtained from
the hydrogenolysis of cellulose or 1,4-anhydroerythritol.[16]
A new route was developed for the direct synthesis of
dodecanol and jet fuel ranged branched alkane with MIBK which
can be obtained from lignocellulose. The reactions were
conducted by dual-bed catalyst systems. In the first bed, the
MIBK was condensed into a mixture of C12 ketone and C12
alcohol (C12 oxygenates). Among the investigated catalysts, the
Pd0.02-MgAl-HT catalyst demonstrated the best performance.
Over it, 73.0% carbon yield of C12 oxygenates was achieved at
553 K and 0.6 MPa. In the second bed, the condensation
products generated in the first bed were further hydrogenated to
dodecanol over the Ru/C catalyst or hydrodeoxygenated to
2,4,8-trimethylnonane (a jet fuel range C12 branched alkanes)
over the Cu/SiO2 catalyst. High carbon yields (~70%) of
dodecanol and 2,4,8-trimethylnonane were achieved by the
dual-bed catalyst systems. The dual-bed catalyst systems were
stable under invesigated conditions. No evident deactivation was
80
60
Carbon yield of dodecanol
Carbon yield of MIBC
40
20
0
0
3
6
9
12
15
18
21
24
Time on stream / h
Figure 3. Carbon yields of dodecanol (▲) and MIBC (▼) from the reaction of
MIBK and hydrogen over the dual-bed catalyst system of Pd0.02-MgAl-HT and
5wt.% Ru/C. Reaction conditions: 0.6 MPa H2, 1.0 g Pd0.02-MgAl-HT for the
first bed (553 K) and 1.0 g 5wt.% Ru/C for the second bed (373 K), hydrogen
flow rate: 150 mL min−1, MIBK flow rate: 0.05 mL min−1
.
As the final aim of this work, we explored the possibility for
the direct synthesis of dodecanol and jet fuel range branched
alkane with MIBK and hydrogen over dual-bed catalyst systems.
In the first bed, MIBK was condensed to C12 oxygenates over
the Pd0.02-MgAl-HT catalyst under the optimal reaction
conditions (553 K and 0.6 MPa H2). In the second bed, the C12
oxygenates generated in the first bed was further
hydrogenateded to dodecanol when 5wt.% Ru/C was used as
the catalyst (see Figure S9 in supporting information). The
carbon yield of dodecanol from such a dual-bed catalyst system
is about 70% which is very close to the carbon yield C12
oxygenates (73.0%) in the first bed. As potential applications,
the dodecanol as obtained can either be sulphated to produce
dodecylsulphate (SDS)[8] or be dehydrated to dodecene wich is
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10.1002/cssc.201601563
ChemSusChem
COMMUNICATION
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (no. 21277140; 21476229; 21506213;
21690082; 21690084), Dalian Science Foundation for
Distinguished Young Scholars (no. 2015R005), the Strategic
Priority Research Program of the Chinese Academy of Sciences
(XDB17020100), Department of Science and Technology of
Liaoning Province (under contract of 2015020086-101) and 100-
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Keywords: Aldol reaction
hydrodeoxygenation • jet fuel
•
biomass
•
dodecanol
•
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10.1002/cssc.201601563
ChemSusChem
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
For the first time, dodecanol and jet
fuel range C12 branched alkane were
directly synthesized in high carbon
yield (~70%) by dual-bed catalyst
systems with hydrogen and methyl
isobutyl ketone which can be derived
Xueru Sheng, Ning Li,* Guangyi Li,
Wentao Wang, Aiqin Wang, Yu Cong,
Xiaodong Wang and Tao Zhang*
Page No. – Page No.
Direct Synthesis of Renewable
Dodecanol and Dodecane with Methyl
Isobutyl Ketone over Dual-Bed
Catalyst Systems
((Insert TOC Graphic here))
Feedstock for surfactants
from lignocellulose.
+ H2
MIBK
This article is protected by copyright. All rights reserved.