Obtaining a high value branched bio-alkane from biomass-derived levulinic acid using RANEY as hydrodeoxygenation catalyst

Article abstract of DOI:10.1039/c6ra14625b

Compared to 5-HMF (C₆H₆O₃), angelica lactone (C₅H₆O₂) is a platform compound that has more potential for biomass-derived high performance bio-alkane fuel production due to a CC bond in the molecular structure, leading to a C-C coupling intermediate (C10 self-aggregation dimer) and higher C:O ratio (2.5), resulting in lower hydrogen consumption for the subsequent hydrodeoxygenation process. Biomass-derived levulinic acid was used as the only starting raw material to produce C10 branched alkanes. First, carboxyl and carbonyl functional groups of levulinic acid under catalysis via intramolecular esterification and dehydration yielded angelica lactone, which included two isomers of angelica lactone (α-angelica lactone and β-angelica lactone). Secondly, angelica lactone di/trimers would be obtained by angelica lactone self-aggregation: α-angelica lactone and β-angelica lactone connecting via C-C bond coupling. Finally, these intermediate products are selectively hydrodeoxygenated over a RANEY catalyst to obtain C7-C10 branched alkanes. Nearly a 90% yield can be achieved under 483 K and 5 MPa H₂ and the C10 branched alkane product, 3-ethyl-4-methyl heptane, accounts for 75% of the same.

Full text of DOI:10.1039/c6ra14625b

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Obtaining high value branched bio-alkane from biomass-derived
levulinic acid using Raney nickel as hydrodeoxygenation catalyst
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a,b
a,b
a
a
a
Boqiong Lu
,
Jinlong Li , Guangqiang Lv , Yongqin Qi , Yingxiong Wang , Tiansheng Deng ,
a*
a*
Xianglin Hou and Yongxing Yang
DOI: 10.1039/x0xx00000x
6 6 3 5 6 2
As compared with 5-HMF(C H O ), angelica lactone (C H O ) is a more potential platform compound for biomass-derived
www.rsc.org/
high performance bio-alkanes fuel production due to its premium C=C bond in the molecular structure, leading to the C-C
coupling intermediate (C10 self-aggregation dimer); and higher C:O ratio (2.5), leading to lower hydrogen consumption for
the subsequent hydrodeoxygenation process. Biomass-derived levulinic acid is used as the only starting raw material to
produce C10 branched alkanes. First, carboxyl and carbonyl functional groups of levulinic acid under the catalysis via
intramolecular esterification dehydration yields angelica lactone, which includes two isomers of angelica lactone (α-
angelica lactone and β-angelica lactone). Secondly, angelica lactone di/trimers would be obtained by angelica lactone self-
aggregation: α-angelica lactone and β-angelica lactone connect via C-C bond coupling. Finally, these intermediate products
are selectively hydrodeoxygenated over Raney nickel catalyst to obtain C7-C10 branched alkanes: nearly 90% yield can be
achieved under 483 K and 5 MPa H
2
; C10 branched alkane product 3-ethyl-4-methyl heptane accounts for 75%.
1
. Introduction
with high carbon number, high energy density and high value
from the cellulose sources is the critical challenge to the
Biomass represents an abundant carbon-neutral
4
biofuel research area .
renewable resource for the production of bioenergy and
biomaterials, which is the sole renewable carbon source of
1
liquid fuel . Cellulose accounts for 75% of the biomass
5-hydroxymethyfurfural (5-HMF) derived from six carbon
sugar dehydration has been envisaged as an important
platform compound for biofuel production in biorefinery
5
processes . C-C bond coupling can be achieved by aldol
resources in nature, constituting the main fraction of biomass
resources which is up to significantly improve carbon
utilization. Sugar derivatives from cellulose degradation can
synthesize high performance fuel and a variety of high value
condensation, owning to the coupling reaction between
aldehyde functional group with ketones, alcohols and other
2
6
functional groups . Further, high carbon number hydrocarbons
green chemicals , which is of great significance and profound
7
C9) could be obtained by HDO process . As
impact for academic and industry, especially for the
sustainable development of human society. But the traditional
thermal cracking combined with hydrodeoxygenation (HDO)
components (
≥
compared with 5-HMF, levulinic acid is a more promising
platform compound. Relying on its rich intramolecular
functional groups, carbonyl and carboxyl functional groups,
levulinic acid can get rid of one oxygen atom by the unique
intramolecular esterification reaction to form angelica lactone,
which need no hydrogen consumption. So the C:O ratio (2.5) of
process only yields low carbon number components (
≤C6),
limiting the product value due to the low energy density and
3
causing a great waste of biomass resources . Therefore,
exploring new reaction path to get hydrocarbon compounds
angelica lactone (C
5 6 2
H O ) is higher than the ratio (2.0) of 5-
6 6 3
HMF (C H O ), which is very beneficial to the subsequent HDO
step due to lower hydrogen cost. It is another hydrogenation
8
route that levulinic acid could also produce GVL. On the other
hand, the valuable C=C bond in the molecular structure of
angelica lactone will lead to the C-C coupling and the self-
aggregation dimer (C10) formation. Angelica lactone is a more
potential platform compound than 5-HMF based on decreasing
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hydrogen cost consideration for high carbon number alkane
production from biomass sources.
2
. Experimental
As for the HDO step, the first studies on the use of
supported nickel for the hydrogenation/hydrogenolysis of
Levulinic acid (99 wt%) is purchased from langfang haoke
2
b
technology co, LTD.; Alpha angelica lactone 97% (GC grade) is
purchased from Sahn chemical technology (Shanghai) co, LTD.;
Anhydrous potassium carbonate, anhydrous ethanol,
cyclohexane, decahydronaphthalene, petroleum ether, ethyl
acetate and phosphate acid are purchased from Tianjin
Kemiou Chemical Reagent Co, LTD.
sugars and polyols date back to the 1930s . As a consequence
of the recent interest in biofuels, many HDO catalysis systems
9
of biomass-derived intermediates have been explored .
Supported-noble metals and nickel have been usually used as
1
0
HDO catalysts . Mark Mascal has adopted Cu-ZnO, Pt-ReOx,
ReOx and Ir-catalysts for the HDO of cyclic esters and obtained
4
c
Raney nickel catalyst characterization and evaluation
The Raney nickel is provided by Hangzhou Fangsheng
Chemical Co., Ltd. The XRD patterns of the catalyst is recorded
with a Philips PW 3040/00 X’Pert MPD/MRD diffractometer
branched alkanes . Zhang’s result shows that Pd/C is effective
for oxygen removal, and his co-workers also uses silica-
alumina supported nickel catalyst for the HDO of angelica
4
b, 11
lactone dimer and trimer
. Dumesic has discovered a
using Cu Kα radiation operated at 45 kV and 40 mA. N
2
heterogeneous catalyst based on Ni, Sn and Al, which is active
and selective for the production by aqueous-phase reforming
adsorption-desorption isotherms are determined at 77K on a
Micromeritics TriStar 3000 instrument. The catalyst is first
degassed under vacuum at 353K for 8 h. Scanning Electron
Microscopy (SEM) is measured on a JSM-7001F microscope.
The TEM (Transmission electron microscope) is conducted on a
JEM-2100F microscope. Temperature programmed reduction
1
2
of ethylene glycol, glycerol, and sorbitol . Serrano studies
catalytic conversion of rapeseed oil into raw chemicals and
fuels over Ni- and Mo-modified nanocrystalline ZSM-5 zeolite,
and his co-workers also studies the effect of metal and support
properties on bio-oil model compound anisole HDO over
1
3
(H
750, Micromeritics). The sample (0.25g) is submitted to a
heat treatment (from room temperature to 900 °C with 10
C/min) in a gas flow (20 mL/min) of the mixture N :H (volume
2
-TPR) is carried out in an automatic equipment (Chemisorb
supported Ni and Co catalysts . Raney nickel, a spongy bulky
metal nickel catalyst, exhibits particular catalytic performance
and has been often used for many hydrogenation or
hydrogenolytic cleavage reactions. It has higher activity due to
its more active sites per volume or weight and needs milder
conditions for the hydrogenation process even as compared
with some noble metals catalysts. In particular, its surface
defect sites could act as special active sites, leading to its
exceptional catalysis performance. For example, Raney nickel
offer high efficiency and selectivity in molecular hydrogen
2
°
2
2
ratio = 95:5). XPS is performed under an ultrahigh vacuum on a
Kratos AXIS ULTRA DLD spectrometer with Al K radiation and a
multichannel detector.
3
. Results and discussion
1
4
Levulinic acid dehydration
activation . It has been used for the hydrogenation of d-
glucose, and the kinetics of the hydrogenation of xylose over
15
Raney nickel has also been reported . But the HDO of big C-C
bond coupling molecule (C10) from biomass-derived platform
compound has never been reported.
Levulinic acid intramolecular dehydration could generate
angelica lactone; while angelica lactone will hydrolyze back into
levulinic acid. The levulinic acid and angelica lactone are in the state
1
6
In this study, a 3-steps preparation process starting from of equilibrium (as shown in Scheme. 2(a)) . If angelica lactone
levulinic acid is present to obtain high value C10 branched bio- could be separated from the reaction system, the equilibrium will
alkanes (as shown in scheme 1). Commercial Raney nickel is be beneficial to the angelica lactone formation and the reaction
conversion can be improved greatly. Because the boiling point
difference between angelica lactone and levulinic acid is big enough
used as the catalyst for the HDO step.
Scheme. 1 Reaction pathways the conversion of levulinic acid into bio-alkanes
2
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(levulinic acid boiling point is 518K, and angelica lactone present in the molecular structure of both α-angelica lactone
boiling point is 440K), reduced pressure distillation method is and β-angelica lactone could combine, leading to self-
employed to separate the angelica lactone from the aggregation intermediates (as shown in scheme.2 (b)). Zhang
2 3
equilibrium reaction system. In present work, an in-situ uses anhydrous K CO as the catalyst and the yield reach about
separation setup is built by using packed column distillation for 90%, as for products distribution, the di/tri/tretramers ratio is
4
b
the separation of angelica lactone from the equilibrium 6:3:1 . In our study, the optimal reaction conditions are
system: levulinic acid is refluxed into the reaction system, and determined as follows: reaction temperature 353K, 10wt%
angelica lactone is condensed through the cold pillars for
2 3
K CO . Under these conditions, both the conversion and the
collection. This process is designed to separate the generated yield to dimer/trimer for the angelica lactone self-aggregation
angelica lactone from reaction system in time, avoiding further could reach nearly 100%. Especially, the dimer product
side-reaction of angelica lactone during reaction process and dominates (75%) (as shown in FigS1). In this process, we can
favoring the equilibrium towards angelica lactone. We carry obtain nearly 7.5g angelica lactone dimer from 10g angelica
out the levulinic acid dehydration reaction at different lactone. The ESI Fig. 2 shows a typical mass spectrum of
3 4
pressure by employing different concentrations of H PO as products in negative ion modes for MALDI MS analysis of
the catalyst under different temperature. The results are products with a time-of-flight (TOF) mass spectrometer.
summarized in Table 1. The optimal reaction conditions are Besides the peaks originated from matrix, two peaks are
3 4
determined as follows: 9KPa, 453K, 3 wt% H PO . Under these observed at m/z 196 and 294, corresponding to the angelica
conditions, the yield of angelica lactone could reach 60%. The lactone self-aggregated products: dimer and trimer,
1
process could yield 120g angelica lactone from 200g levulinic respectively. Furthermore, C NMR are further applied to
3
acid.
confirm the chemical structures of products, which are shown
in compounds are found to be (as shown in FigS4). The tertiary
and quaternary carbon would be distinguished as compared to
Angelica lactone self-aggregation
1
3
dept135- C NMR (as shown in FigS5). Herein, we proposed
the mechanism as followed: the ratio of α-angelica lactone and
β-angelica lactone is almost 6:4 before the reaction. Under the
anhydrous K CO presence, α-angelica lactone is isomerized to
It is well known that angelica lactone has two isomers: α-
angelica lactone and β-angelica lactone. α-Angelica lactone will
further isomerize to produce β-angelica lactone in the
presence of catalysts at high temperature. The two isomers
also are in the state of equilibrium (as shown in scheme.2 (b)).
Under different catalysis system, the C=C bonds
2
3
β-angelica lactone because of alkaline catalysis effect. At the
same time, C-C bond split took place for both α-angelica
lactone and β-angelica lactone: C3-H of α-angelica lactone
broke and C4-H of β-angelica lactone broke, then the dimer
produced. When there is substituent group in C4 of β-angelica
lactone, C3-H split also happened for β-angelica lactone. In the
same way, for the dimer C3-H split took place as well. So dimer
and β-angelica lactone could combine into trimer by C-C
coupling (as shown in scheme.2 (b)).
Table 1. The temperature and catalyst influence on the yield of
angelica lactone
LA produced into AL under 9KPa by 1wt%, 3wt% and 5wt%
H PO as catalyst at 443K;
3
4
LA produced into AL under 9KPa by 3wt% H PO as catalyst at
4
3
443K, 453K and 463K.
LA produced into AL by 3wt% H PO as catalyst at 453K under
3
4
(a)
(b)
6, 9, 12KPa.
No.
1
H
3
PO
4
(wt %)
T[K]
443
443
443
443
453
463
453
453
453
Yield[%]
22
1
2
3
5
3
3
3
3
3
3
53
3
45
4
48
5
60
6
58
7
59
8
60
Scheme. 2 (a) The equilibrium of angelic lactone and levulinic
9
49
acid (b) The mechanism of angelic lactone self-aggregation
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Hydrodeoygenation
which has high octane number (RON, 155) and low freezing
point (FP, 190 K), and is an important component of high
performance jet fuel. The excellent yield to this C10 product
results from the mild reaction temperature (463K). Under this
temperature, Raney nickel could selectively activate the C-O
bond hydrogenolysis and effectively remove the oxygen,
meanwhile the cracking side-reaction of C-C bond could be
depressed and is not significant. For many hydrotreatment
reactions, decahydronaphthalene is proved to be an efficient
solvent that is capable of transferring hydrogen, enabling the
Raney
nickel
has
been
often
used
for
hydrogenation/hydrogenolysis reaction and has attracted lots
of attentions due to its low cost, high efficiency and milder
application conditions, which is understandable from the
economic point of view (the energy input, hydrogen cost and
the catalyst lifetime). In present work, a nearly 100 %
conversion could reach for the HDO of the angelica lactone
self-aggregation intermediates over the Raney nickel catalyst.
Because the Raney nickel catalyst could be dispersed in the
liquid phase of decahydronaphthalene very well and the three
dimensional free rotation of the catalyst particles in the liquid
phase could be achieved. All of the active sites present over
the bulky Raney nickel surface could be accessible to the HDO
activation, which can improve the catalytic efficiency
significantly. Traditional supported catalysts are limited in
activity due to the amount of active metals that can be
deposited on the pore walls of a support. Bulky Raney nickel
could sidestep this constraint - it is predominantly metal that
contains porosity. Raney nickel catalyst could bear higher
density of active sites and higher specific activity per volume
unit. On the other hand, the HDO reaction over Raney nickel is
very sensitive to temperature and lower temperature will
result in the significant drop for the Raney nickel catalytic
performance. For example, at 463K the HDO product
conversion is 51%, decreasing by 40% as compared with the
temperature at 483K. In present work, the Raney nickel
catalyst also display excellent reusability. After five cycles of
the catalyst, a high conversion above 93% still remains.
1
7
conversion to enhance greatly . In our study, it is also found
that the solvent effect is obvious: if the cyclohexane acts as
solvent, the conversion will decrease by 30% at the same
condition. It is clearly that decahydronaphthalene is more
advantageous in HDO reaction for Raney nickel system due to
the hydrogen-donating benefit. Michael Coleman found that
the classical hydrogen-donating solvent also is excellent high-
temperature thermal stabilizer that could inhibit efficiently the
1
8
thermal cracking of side-reaction . In present work, the
thermal stabilization effect of the decahydronaphthalene
solvent also contributes to the minor “cracking” products (less
2
5%). Hanford used Raney nickel catalyst for the
1
9
hydrogenolysis of monosaccharides into glycols and glycerol .
In his study he claimed an improvement to the process and the
possibility of running it under milder conditions by introducing
the Raney nickel catalyst. The C-C bond of the tertiary carbon
structure will be susceptible to the cleavage. In our study, the
decarboxylation freed from the tertiary carbon structure of
angelica lactone dimers will lead to the C9 (C10-C9) products
and the ethyl group cleavage will lead to the C8 (C10-C8) and
All of the HDO products are saturated branched alkanes
according to GC result (as shown in Fig. 1). Raney nickel
catalyst could yield a narrow product distribution: C7 (4.92%),
C8 (9.16%), C9 (10.27%), C10 (75.65%). The main product is
high value C10 branched alkane: 3-ethyl-4-methyl heptane,
4
c
C7 (C9-C7)
.
Physicochemical characterization of the catalysts
The X-ray diffraction patterns of Raney nickel is displayed
in Fig. 2(a). The XRD pattern of the commercial Raney nickel is
concordant with typical crystalline Ni, having diffraction peaks
2
2
1
1
50000
00000
50000
00000
C8
C9
o
at 46.2 and 51.5 , corresponding to Ni (111) and Ni (200),
respectively. The catalyst is produced by alkaline leaching of
aluminum from nickel-aluminum alloy, which consists of Ni Al
C10
C7
2
3
0
2
and NiAl
3
intermetallic phases and pure aluminum .
Therefore, it is possible that the long time spent in the
leaching process (about 8 h) promoted an almost completed
dissolution of the other phases in Raney nickel catalyst. Fig.2
5
0000
0
1
0
15
20
25
Time(min)
30
35
40
2
(b) shows the H -TPR spectra from room temperature to 900
C7
C8
C9
°C of the Raney nickel catalyst. The sharp hydrogen
consumption peaks which
75.65%
C10
4
00
50
00
50
(
a)
3
(b)
3
Ni
°
2
4.92%
10.27%
9.16%
200
150
100
Ni
°
Ni
°
Ni
°
Ni
°
50
Fig. 1 (a)GC chromatogram of hydrodeoxygenation of angelica
0
lactone di/trimerization products.
35 40 45 50 55 60 65 70 75 80 85
o
-50
-
100
0
100 200 300 400 500 600 700 800 900 1000
Temperature(
2θ( )
°)
(b)Products distribution of the HDO of angelica lactone
di/trimers
Fig. 2 (a) XRD pattern of the Raney nickel catalyst.
4
| J. Name., 2012, 00, 1-3
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ARTICLE
(
b) H
are located at about 100 °C can be assigned to hydrogen
adsorption of skeletal nickel. The H -TPR result illustrates that
2
-TPR patterns of the Raney nickel catalyst.
(c)(d)TEM images of the Raney nickel catalyst.
4
3
2
1
0
0
0
0
0
0.010
2
2
BET Surface Area: 37.2554 m /g
3
Total Pore Volume:0.061662 cm /g
0.008
the Raney nickel is present in several states with different
reducibility. The reduction peaks around 300 °C can be
assigned to the reduction of nickel clusters. According to the
results of Fig.3, hydrogen consumption peaks of nickel ranged
from 500 to 700 °C indicated that nickel can be generated even
though calcination temperature is merely 800 °C. Furthermore,
it is remarkable that the sharp hydrogen consumption peaks
before 170 °C can be assigned to hydrogen adsorption of
skeletal nickel.
0.006
0.004
0.002
0.000
0
.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0
5
10 15 20 25 30 35 40 45
Pore Diameter(nm)
P/P0
Fig. 4
2
N adsoption-desoption isotherms of the Raney nickel
catalyst.
Fig. 3(a) (b) displays the SEM of Raney nickel catalyst. The
SEM images show that the Raney nickel has relatively smooth
surface and large particle size. There are some cracks on the
surfaces of the catalysts, which are caused by the leaching of
aluminum. The sample has abundant microstructures and
modest dense agglomerate while there are some grains. The
sample is made up of several blocks with different-sized
particles inserting on them. It is possible to observe the
sponge-like morphology of the Raney nickel catalyst,
presenting pores <50 nm and some porous type slits. Details of
the catalyst morphology could be better visualized by TEM.
The TEM of the Raney nickel catalyst are given in Fig. 3(c) (d).
Ni3p Al2p
Ni2p3/2
Ni2p1/2
metal oxide
metal oxide
6
0
65 70 75 80 85
Binding Energy(eV)
840
850
860
870
880
890
Binding Energy(eV)
The figure shows the spongy structure of the Raney nickel, Fig. 5 XPS spectra of Ni 2p, Ni 3p, Al 2p.
formed by small nickel domains with no defined shape.
Textural properties of the sample are obtained from the
N2 sorption isotherms, which are displayed in Fig. 4. The
Conclusions
adsorption isotherms of the sample are the typical of
mesoporous materials (diameters in the range of 5-20 nm).
In this study, biomass-derived levulinic acid used as the
only starting raw material could be transformed into high
value C10 branched bio-alkane via 3 steps. As compared with
2
The BET surface area is about 37m /g. XPS can give
information on the chemical compositions of the catalyst in
the upper layers from the sample surface in Fig. 5. The catalyst
still contained both the metallic and oxide states of nickel and
aluminum. Furthermore, the nickel also exists in two states of
5
-HMF, angelica lactone is a more potential platform for C-C
bond coupling. Raney nickel catalyst dispersed in the
decahydronaphthalene could display very high activity at mild
temperature, depressing the C-C breaking side-reaction
significantly.
m
e
t
a
l
l
i
c
n
i
c
k
e
l
(
N
i
2
p
3
/
2
a
t
8
5
6
.
3
e
V
)
a
n
d
n
i
c
k
e
l
o
x
i
d
e
(
N
i
2
p
3
/
2
at 861.0 eV). Aluminum oxide (Al 2p at 74.4 eV) could be
detected on the Raney nickel surface.
(
a)
(b)
Acknowledgements
This work received financial support from the Natural
Science Foundation of China (21403273), the National Key
Basic Research Program of China (973 Program)
(
(
2012CB215305), the Shanxi Scholarship Council of China
2015-122) and the Department of Human Resource and Social
Security of Shanxi Province (Y6SW9613B1).
(c)
(d)
Notes and references
1
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Davison; George Britovsek; John Cairney; Charles A. Eckert;
William J. Frederick Jr.; Jason P. Hallett; David J. Leak; Charles L.
Liotta; Jonathan R. Mielenz; Richard Murphy; Richard Templer;
Tschaplinski, T., The Path Forward for Biofuels. SCIENCE 2006,
3
11, 484-489; (b) Laskar, D. D.; Tucker, M. P.; Chen, X.; Helms, G.
Fig. 3 (a) (b) SEM images of the Raney nickel catalyst.
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9. Furimsky, E., Catalytic hydrodeoxygenation. Applied
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2
2. (a) Serrano-Ruiz, J. C.; Luque, R.; Sepulveda-Escribano, A., hydrogenation and hydrodeoxygenation of biomass-derived
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Zn/Al2O3 Catalyst for the Hydrogenation of Esters to Alcohols.
Chinese Journal of Catalysis 2010, 31 (7), 769-775; (c) Jason M.
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PleaseRd So Cn oA t da vd aj un s ct ems argins
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DOI: 10.1039/C6RA14625B
Journal Name
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DOI: 10.1039/C6RA14625B
O
O
OH Dehydration
C-C bond
O
Raney nickel HDO
O
+
O
O
C10H
22
C9H20
O
O
O
O
Levunlinic acid
Angelica Lactones
C5
H8O3
C
5H6
O2
Dimer
C8
H18
C7H16
C7
(a)
(b)
C8
C9
C10
75.65%
4.92%
1
0.27%
9.16%