Catalytic deoxygenation of liquid biomass for hydrocarbon fuels

Kyung C. Kwon
a,
*
, Howard Mayeld
b
, Ted Marolla
b, c
, Bob Nichols
c
, Mike Mashburn
d
a
Chemical Engineering Department, Tuskegee University,Tuskegee, AL 36088, United States
b
AFRL, Tyndall Air Force, Panama City, Florida, United States
c
Applied Research Associates, Inc, Panama City, Florida, United States
d
Physics Department, Florida State University, Tallahassee, Florida, United States
a r t i c l e i n f o
Article history:
Received 19 February 2009
Accepted 8 September 2010
Keywords:
Canola oil
Methyl laurate
Liquid biomass
Deoxygenation
Liquid hydrocarbon fuel
a b s t r a c t
Liquid biomass such as methyl laurate and canola oil is deoxygenated with hydrogen and NiMo/g-Al
2
O
3
catalyst. Oxygen from methyl laurate and canola oil is removed at 18.25e85.13 bar initial cold hydrogen
pressure and 300e400

C, using a 316 stainless steel batch reactor. Removal of oxygen from liquid methyl
laurate and canola oil is evaluated with a GC/MS analyzer for liquid reaction products and another GC for
gaseous reaction products. The range of reaction duration of liquid biomass in the batch reactor is 30
e60 min under the deoxygenation conditions. Conversion of liquid biomass into gaseous products is
evaluated with analysis data of gas products and a mass balance in terms of hydrogen.
The objective of this research is to develop an efcient method of removing oxygen from liquid
biomass to produce petroleum-comparative liquid hydrocarbons with hydrogen and a catalyst.
Removal of oxygen from bio-based fuels for liquid hydrocarbon fuel is needed to increase its energy
intensity, stability, and decrease its viscosity. In this paper, removal of oxygen from methyl laurate and
canola oil is discussed in detail in terms of various oxygen removal conditions such as reaction
temperature and pressure, catalyst amount, and hydrodynamics of heterogeneous reaction mixture in
the batch reactor.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Conversion of liquid biomass to hydrocarbon fuels is the
primary step in rening liquid biomass produced from vegetable
oils, animal fats, biodiesels, and waste cooking oils. Removal of
oxygen from biofuels is needed to enhance fuel enthalpies,
decrease viscosity of biofuels, and stabilize biofuels.
Various catalysts in addition to NiMo/g-Al
2
O
3
and CoMo/g-
Al
2
O
3
are well known for deoxygenating liquid biomass; however,
these catalysts are formulated and tested mostly for rening and
hydro-cracking petroleum products. Research is needed in the
development of dual function catalysts suitable for both deoxyge-
nizing and isomerizing functions. The objective of this research is to
develop an efcient method of removing oxygen from liquid
biomass to produce petroleum-comparative liquid hydrocarbons.
Consumption of hydrogen and conversion of liquid biomass into
gaseous products are evaluated by analyzing gaseous reaction
products and making a mass balances on gaseous reaction products
including hydrogen.
Currently, most diesel fuels are petroleum distillation products.
The earths supply of oil will be exhausted and crude oil availability
will diminish in the future, and a new energy source is needed to
supplement alternative petroleum [1]. Environmental concerns
and diminishing petroleum reserves have also increased the
importance of biofuels. Biofuels produced from wood, vegetable
oils and animal fats have been considered promising for delivering
biofuels in large amounts. The abundance of oxygen in the form of
various aliphatic and aromatic oxygenates decreases the quality of
biofuels. Therefore, the oxygen content of biofuels must be reduced.
Upgrading of biofuels can be achieved by hydrodeoxygenation, in
which oxygen-containing biomass is converted to hydrocarbons by
eliminating oxygen in the form of water in the presence of
hydrogen and sulded catalysts [2].
Many researchers have tried to produce biofuels from abundant
renewable biomass as well as waste materials with hydrogen and
sulded catalysts. Craig et al. described a process for producing
hydrocarbon products in the diesel boiling range, comprising
mainly C
15
eC
18
parafns and being highly effective as diesel fuel
ignition improvers. The process comprises hydroprocessing vege-
table oils such as canola, sunower, soybean, and rapeseed oils or
some fatty acids at 350e450

C, 4.8e15.2 MPa, and the liquid
hourly space velocity (LHSV) of 0.5e5 h
1
, using commercially
* Corresponding author. Tel.: 1 334 727 8976/724 4528.
E-mail address: kwonk@tuskegee.edu (K.C. Kwon).
Contents lists available at ScienceDirect
Renewable Energy
j ournal homepage: www. el sevi er. com/ l ocat e/ renene
0960-1481/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2010.09.004
Renewable Energy 36 (2011) 907e915
available hydroprocessing catalysts such as CoeMo catalysts and
NieMo catalysts were used [3].
Monnier et al. described a process for producing fuel ignition
improvers for diesel fuels having high cetane numbers, using
a trickle-bed reactor. Biomass feedstock for the process includes tall
oil, wood oils, animal fats, and vegetable oils. The catalysts suitable
for the process are commercial hydroprocessing catalysts, including
CoeMo catalysts, NieMo catalysts, and other transition metal
based catalysts. Carbon disulde was used to avoid loss of sulded
active sites on the catalyst surface and maintain catalyst activity [4].
ChowandW. Peng producedliquidsynthetic crude petroleumby
catalytically cracking a biomass material comprising plant oils,
animal oils, and rubber, using a catalyst and a carrier gas such as air,
nitrogen, argon, helium, and hydrogen. The catalyst comprises
aluminawithor without a component chosenfromsilica, crystalline
aluminosilicate zeolites, rare earth oxides, and sodium oxide [5].
Liquid biomass such as methyl laurate, canola oil and its bio-
diesel, spent waste kitchen oil and its biodiesel, NSWC-02 biodiesel
(6/13/08), Energy BLD 9738 biodiesel (1/8/08), and Wallace bio-
diesel (7/14/2008) was deoxygenated in a 35-cm
3
batch reactor
with hydrogen and NiMo/Al
2
O
3
catalyst at 300e400

C and
17.24e86.18 bar. The liquid reaction product was analyzed with
a GC/MS, whereas the gaseous reaction product was analyzed with
a GC. Hydrogen consumption and conversion of liquid biomass to
gaseous products were investigated during the deoxygenation and
isomerization of liquid biomass [6].
Many researchers have also tried to produce bio-oils from
abundant renewable biomass as well as waste materials with the
fast pyrolysis method instead of the catalytic deoxygenation
method using both hydrogen and sulded catalysts.
Su-Ping Zhang et al. produced bio-oil from the fast pyrolysis of
biomass. Bio-oil has a high oxygen content. Produced bio-oils
contain ketones and aldehydes, carboxylic acids, esters, aliphatic
and aromatic alcohols, and ethers in signicant quantities. The
reactivity of oxygenated groups presents a problem with stability.
Therefore, more study of the deoxygenation of bio-oils is needed,
using hydrogen and cobalt molybdate catalyst [7].
Bio-oils produced from fast pyrolysis liquids of biomass are
complex mixtures of oxygen-containing compounds. Their high
oxygen content is responsible for high viscosity, poor thermal
stability, lowheating value, and corrosivity. These properties can be
improved by partial or total elimination of oxygen, and hydroge-
nation and isomerization of chemical structures. Hydro-
deoxygenation of bio-oils was carried out at high temperature and
pressure with alumina supported sulded CoMo and NiMo cata-
lysts. Three process methods such as high-pressure thermal treat-
ment, catalytic decarboxylation, and catalytic hydrodeoxygenation
were examined for the removal of oxygen from bio-oils. Guaiacol,
isopropanol, naphtol, and benzoquinone were selected as the
model compounds to simulate upgrading bio-oils [8].
Wood-based biomass is one renewable alternative for the
production of transport fuels. The crude from pyrolysis and lique-
faction of wood-based biomass, known as bio-oil, contains various
oxygen functionalities such as carboxyl, carbonyl, hydroxyl and
methoxy groups. In addition, water is present in large amounts. The
total oxygen content of bio-oils may thus be as much as 50 w%.
Because of the deleterious effects of high oxygen content on fuel
properties such as thermal and chemical stability and miscibility
with hydrocarbons, bio-oils must be upgraded by reducing their
oxygen contents. The upgrading can be achieved with hydro-
treating catalysts similar to those used for hydrodesulphurization
in oil reneries [9].
Catalysts for the deoxygenation of biomass are formulated by
impregnating active catalytic metals into catalyst supports, and by
drying and calcining impregnated catalysts.
CoMo/carbon hydrooxygenation catalysts were prepared using
a commercial activated carbon as a support. The support was
impregnated with aqueous solutions of ammonium heptamo-
lybdate and cobalt nitrate, using the incipient wetness method.
Molybdenum was impregnated rst and cobalt second. After each
impregnation, the sample was dried under argon owat 130

C and
calcined at 400

C for 3 h [10].
The catalyst composition of the invention (WO/2007/141293) is
characterized by a low loading of the active metal components,
with the preferred metal content of the catalyst composition being
in the range from 5 to 20 wt%. This low loading does not sacrice
catalytic activity for the hydrodeoxygenation of biomass. It also
limits uneven distributions of active metals, and facilitates efcient
co-action of the two or more metal components. A usual method
for distributing catalytically active materials over the surface of
particulate carrier material comprises impregnating the carrier
material with a solution of a precursor of the desired metal, drying,
and calcining the impregnated carrier material to convert the
deposited metal into the corresponding metal oxides. The
impregnating solution may contain a phosphorous compound, such
as phosphoric acid, to enhance the stability of the solution. During
the hydrodeoxygenation process, the rapeseed oil is converted
mainly to C17 and CeC18 parafns with propane, water, carbon
dioxide, and carbon monoxide as by-products [11].
Catalysts can be prepared withthe incipient wetness technique or
absorption from solutions. The former method comprises impreg-
nation of a porous carrier with a volume of solution, containing the
soluble precursors of the active phases, equal to the volume of the
pores of the carrier used. In this way, the precursors present in solu-
tion are quantitatively absorbed by the carrier. In order to reach the
desired charge of elements, the procedure can be repeated several
times, alternating it with drying. The second method involves
absorptiononthe carrier of the precursors of the active phase starting
from a solution in which the carrier is dispersed [12].
Liquid biomass is processed in multiple processing stages to
reduce consumption of hydrogen, avoid polymerization of liquid
biomass, and keep double bonds of biomass intact, since double
bonds reduce its viscosity and boiling temperature. Liquid biomass
is isomerized to reduce its viscosity and boiling temperature, and
stabilize processed liquid biomass. Isomerization of liquid biomass
carried out either after or before deoxygenation of liquid biomass
[13].
In the Patent WO/2006/075057, renewable biomass is deoxy-
genated by removing oxygen in the form of CO
2
and CO. The
invention relates to a catalytic method for the selective manufac-
ture of hydrocarbons for diesel fuel fromrenewable sources such as
plant/vegetable oils and their fats, and animal/sh oils and their
fats, by contacting the starting biomass with a heterogeneous
catalyst comprising at least one metal selected from the metals
belonging to the group VIII of the Periodic Table. The heterogeneous
catalyst is pre-treated with hydrogen at 150e250

C. Hydrocarbon
mixtures are isomerized with catalysts such as ferrierite, Pd, Ni,
SiO
2
, and Al
2
O
3
[14].
Bio-based oils are very different fromcrude oils from petroleum
sources. The sulfur content of biocrudes is negligible, whereas bio-
oils are rich in oxygen-containing molecules. Hydrodeoxygenation
(HDO) of bio-oils typically comprises two stages. The rst stage is
carried out at lower reaction temperatures in order to avoid poly-
merization of the oxygen-containing compounds and coking of the
catalyst during the following deoxygenation step. At the second
stage, under more severe reaction conditions, oxygen removal is
efcient and large amounts of hydrogen are consumed. The rst
stage can be applied at lower cost to produce partially deoxygen-
ated fuels suitable for the generation of electricity, heating fuels,
and production of some chemicals [15].
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 908
A feedstock originating from renewable sources is converted to
branched and saturated hydrocarbons in the diesel fuel distillation
range by skeletal isomerization. Deoxygenation is carried out by
hydrodeoxygenation or alternatively by combined decarboxylation
and decarbonylation reactions, whereby the consumption of
hydrogen is decreased. Skeletal isomerization of biomass is carried
out in the presence of an acidic catalyst such as silico alumino
phosphates and zeolites at a temperature of 200e350

C and
0.1e5 MPa. Deoxygenation of biomass is carried out in the presence
of NiMo/Al
2
O
3
or CoMo/Al
2
O
3
catalyst and hydrogen at a tempera-
ture of 250e350

C and 2e10 MPa. Saturated long straight chain
fatty acids (C10:0 and higher) are solid at room temperature, which
makes their processing and use difcult in a number of applica-
tions. Unsaturated long chain fatty acids like e.g. oleic acid are easily
processable liquids at room temperature, but they are unstable
because of double bond. Branched fatty acids mimic the properties
of straight chain unsaturated fatty acids in many respects, but they
are more stable. An objective of the process is to manufacture
branched saturated hydrocarbons from renewable biomass [16].
Biological raw materials contain high amounts of oxygen that is
converted to water, carbon monoxide and carbon dioxide during
processing. Prior to the hydrogenation (HDO) step, the biological
raw material is treated by prehydrogenation under milder condi-
tions thus avoiding side reactions of the double bonds. Prehy-
drogenation is carried out in the presence of prehydrogenation
catalyst at 150e250

C and 10e100 bar. The prehydrogenation
catalysts are Pd, Pt, Ni, NiMo, and CoMo catalyst supported by
alumina and/or silica. In the process for producing a hydrocarbon
component of biological origin, the rst step is hydrodeoxygenation
and the second step is isomerization. In the hydrodeoxygenation
step, hydrogen gas and biological raw material are passed to
a hydrodeoxygenation catalyst bed at 300e400

C and 50e100 bar
to produce n-parafns. After the hydrodeoxygenation step, the
product is subjected to the isomerization step at 300e400

C and
20e30 bar to obtain branched-chain parafns. Biological raw
material such as vegetable oils and fats, animal fats, and sh oils
and their mixtures is subjected to prehydrogenation at 10e100 bar
and 150e250

C prior to the hydrodeoxygenation step. The
hydrogenation catalyst includes Pd, Pt, Ni, NiMo, and CoMo active
metal supported with alumina and or silica, whereas the isomeri-
zation catalyst contains Al
2
O
3
or SiO
2
[17].
2. Experimental setup
Both methyl laurate and canola oil of 2 g are deoxygenated with
initial cold 18.25e85.11 bar hydrogen in the presence of 0e0.2 g
NiMo/Al
2
O
3
catalyst powder and 300e400

C, using a 316 stainless
steel 35-cm
3
batch reactor. The batch reactor is heated with
a Chromalox coil heater, and its temperature is maintained with
a Chromalox temperature controller. The batch reactor is stirred
with a wrist-arm shaker or a water-bath shaker. Removal of oxygen
fromliquid methyl laurate and canola oil is evaluated with a GC/MS
analyzer for liquid reaction products and another GC for gaseous
reaction products. The range of reaction duration of liquid biomass
in the batch reactor is 30e60 min under the deoxygenating
conditions.
2.1. Experimental procedures
Hydrogen is consumed by removing oxygen frombiomass in the
formof H
2
O and CO
2
as well as adding hydrogen to biomass so as to
produce high boiling liquefaction products containing unaccount-
able components, which can not be detected with the GC/MS
analyzer. In this way, the amount of consumed hydrogen can not be
related to the amount of eliminated oxygen.
Initial amounts of hydrogen fed to the batch reactor are obtained
by applying the initial hydrogen pressure and the initial tempera-
ture of hydrogen in the batch reactor to the ideal gas law. Gaseous
reaction products are collected in a sample bag to measure volumes
of gaseous reaction products and analyze concentrations of
hydrogen in gaseous reaction products with a gas chromatograph,
after cooling reaction mixtures to room temperature.
Amounts of hydrogen in gaseous reaction products are obtained
by applying volumes of gaseous reaction products at atmospheric
pressureandroomtemperatureas well asconcentrations of hydrogen
in gaseous reaction products to the ideal gas law. Consumption of
hydrogen during the biomass conversion reaction is calculated by
subtracting amounts of hydrogen in gaseous reaction products from
initial amounts of hydrogen fed to the batch reactor.
3. Results and discussion
3.1. Methyl laurate
Methyl laurate (Fluka, 95 w% purity) of 1.86e2.08 g is deoxy-
genated with initial cold 23.76e47.88 bar hydrogen in the presence
of 0e0.126 g NiMo/g-Al
2
O
3
catalyst for 30 min at 300e375

C, using
a 35-cm
3
batch reactor. Methyl laurate is converted mainly into
undecane (see Equation (1)) and dodecane (see Equation (2)). Lauric
acid is formed as a major intermediate product (see Equation (3)).
Conversion of Methyl Laurate into Undecane
CH
3
(CH
2
)
10
COOCH
3
H
2
/CH
3
(CH
2
)
9
CH
3
CO
2
CH
4
(1)
Conversion of Methyl Laurate into Dodecane
CH
3
(CH
2
)
10
COOCH
3
4H
2
/CH
3
(CH
2
)
10
CH
3
2H
2
O CH
4
(2)
Conversion of Methyl Laurate into Lauric Acid
CH
3
(CH
2
)
10
COOCH
3
H
2
/CH
3
(CH
2
)
10
COOH CH
4
(3)
3.1.1. Temperature
Methyl laurate of 2 g is deoxygenated with initial cold
46.52e47.21 bar hydrogen in the presence of 0.1 g NiMo/g-Al
2
O
3
catalyst for 30 min at 300e375

C. Consumption of reactants such
as methyl laurate and hydrogen and formation of reaction products
such as undecane, dodecane, and CH
4
increase as the reaction
temperature increases over the temperature range of 300e350

C,
as shown in Fig. 1a and b. These experimental data on conversion of
methyl laurate show the temperature dependence of methyl lau-
rate conversion [18]. In addition, this observation suggests that
solubility of hydrogen in liquid reaction mixtures [19] increases
with increased temperatures, and increased concentration of
hydrogen in liquid reaction mixtures results in increased conver-
sion of methyl laurate to undecane and dodecane.
Formation of products such as undecane, dodecane, unac-
countable, and CH
4
, and consumption of hydrogen decrease as the
reaction temperatures increase, whereas formation of unaccount-
able products and intermediate product lauric acid increases as the
reaction temperatures increase over the temperature range of
350e375

C, as shown in Fig. 1a and b. These experimental data
indicate that liquid reaction mixtures are increasingly polymerized
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 909
[15] so as to increase formation of unaccountable as reaction
temperature increases.
Formation of gases generated from liquid reaction mixtures
increases as the reaction temperatures increase over the temper-
ature range of 325e375

C, as shown in Fig. 1c. These experimental
data show that liquid reaction mixtures are catalytically and ther-
mally cracked in the presence of hydrogen and NiMo/g-Al
2
O
3
catalyst so as to increase gaseous products generated from liquid
reaction mixtures as the reaction temperatures increase.
3.1.2. Pressure
Methyl laurate of 2 g is deoxygenated with initial cold
23.77e46.52 bar hydrogen in the presence of 0.1 g NiMo/g-Al
2
O
3
catalyst for 30 min at 350

C. Formation of hydrocarbons such as
undecane and dodecane increases as the initial cold H
2
pressures
increase, as shown in Fig. 2a. This observation suggests that solu-
bility of hydrogen in liquid reaction mixtures [19] increases with
increased hydrogen pressures, and increased concentration of
hydrogen in liquid reaction mixtures results in increased conver-
sion of methyl laurate to hydrocarbons such as undecane and
dodecane. The unaccountable products decrease as the initial H
2
pressures increase, as shown in Fig. 2a.
3.1.3. Catalyst
Methyl laurate of 2 g is deoxygenated with initial cold
46.52e47.90 bar hydrogen in the presence of 0e0.126 g NiMo/g-
Al
2
O
3
catalyst for 30 min at 350

C. Formation of hydrocarbons such

as undecane and dodecane increases as the catalyst amounts
increase, whereas formation of intermediate product lauric acid
and unaccountable products decreases as the catalyst amounts
increase, as shown in Fig. 3a and b. This observation suggests that
both catalysts and hydrogen are needed to convert methyl laurate
to hydrocarbons such as undecane and dodecane.
Methyl laurate is slightlyconvertedinto undecane andlauric acid
inthe presence of hydrogenwithout the catalyst, as showninFig. 3a,
and hydrogen is consumed slightly in the absence of NiMo/g-Al
2
O
3
catalyst, as shown in Fig. 3b. These observations showthat catalysts
are neededtoincrease conversionof methyl lauratetohydrocarbons
such as undecane and dodecane in the presence of hydrogen.
Methyl laurate is slightly converted to undecane and lauric acid
and formation of unaccountable is negligible in the presence of
hydrogen without NiMo/g-Al
2
O
3
catalyst, whereas methyl laurate
is pronouncedly converted to hydrocarbons such as undecane and
dodecane, lauric acid, and unaccountable by adding 0.026-g NiMo/
g-Al
2
O
3
catalyst to the reaction mixture in the presence of
0
20
40
60
80
100
120
1 2 3 4
s
t
c
u
d
o
r
P
n
o
i
t
c
a
e
R
f
o
%
t
h
g
i
e
W
methyl_lau
rate
undecane
dodecane
lauric_acid
unaccount
able
0
5
10
15
20
25
30
35
40
45
1 2 3 4
%
t
h
g
i
e
W
CH4
formation,
w %,
basis on
initial
biomass
H2
consumpti
on, w %,
basis on
initial
biomass
H2
Consumpti
on, w %,
basis on
initial H2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1 2 3 4
g
,
t
h
g
i
e
W
CH4
formation
biomass-
generated
gases in
total gas
product
H2 in total
gas
product
total gas
product
Reaction Temperature,
o
C: 1= 300 2 =325 3 = 350 4 =375
a b c
Fig. 1. Effects of temperature on liquid product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g methyl laurate with 0.1004e0.1053 g catalyst for 30 min at
46.52e47.21 bar initial cold H
2
pressure.
0
20
40
60
80
100
120
1 2 3
L
M
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
undecane
dodecane
methyl_laurate
unaccountable
0
10
20
30
40
50
60
70
80
1 2 3
%
t
h
g
i
e
W
CH4 production,
w %, basis on
initial biomass
H2 consumption, w
%, basis on
initial biomass
H2 consumption,
w %, basis on
initial H2
Initial Cold H
2
Pressure, bar: 1 = 23.77 2 = 36.87 3 = 46.52
a b
Fig. 2. Effects of Initial cold H
2
pressure on product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g methyl laurate (ML) with 0.1-g catalyst for 30 min at 350

C.
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 910
hydrogen. This fact shows that the small amount of the catalyst
promotes formation of undecane, dodecane, lauric acid, and
unaccountable. This observation also suggests that methyl laurate
is signicantly polymerized in the presence of hydrogen and the
small amount of catalyst.
3.1.4. Agitation of reaction mixtures
Methyl laurate of 2 g is deoxygenated with initial cold
46.52e47.90 bar hydrogen in the presence of 0.1 g NiMo/g-Al
2
O
3
catalyst for 30 min at 350

C, as shown in Fig. 4a and b, whereas
methyl laurate of 2 g is deoxygenated with initial cold
46.52e47.21 bar hydrogen in the presence of 0.026e0.027 g NiMo/
g-Al
2
O
3
catalyst for 30 min at 350

C, as shown in Fig. 5a and b.
Formation of undecane and dodecane in the presence of 0.1 g
NiMo/g-Al
2
O
3
catalyst is higher with wrist-action shaking than
horizontal orbital shaking, whereas formation of lauric acid as an
intermediate product and unaccountable is lower with wrist-action
shaking than horizontal orbital shaking, as shown in Fig. 4a.
Formation of CH
4
and consumption of hydrogen in the presence of
0.1 g NiMo/g-Al
2
O
3
catalyst are higher with wrist-action shaking
than horizontal orbital shaking as shown in Fig. 4b. These obser-
vations indicate that hydrodynamics [20] of reaction mixtures
consisting of liquid reaction mixtures, solid catalyst particles, and
gaseous reaction mixtures in the batch reactor affects distributions
of products such as undecane, dodecane, lauric acid, unaccount-
able, and CH
4
, and consumption of hydrogen in the presence of 0.1 g
NiMo/g-Al
2
O
3
catalyst.
Formation of products such as undecane, dodecane, unac-
countable, and CH
4
, and consumption of hydrogen are higher with
wrist-action shaking than horizontal orbital shaking, whereas
formation of the intermediate product lauric acid is lower with
wrist-action shaking than horizontal orbital shaking in the pres-
ence of 0.026e0.027 g NiMo/g-Al
2
O
3
catalyst and 46.52e47.21 bar
initial cold hydrogen at 350

C, as shown in Fig. 5 a and b.
The combined amount of products such as undecane, dodecane,
and lauric acid formed from the wrist-action shaking reaction is
very close to that fromthe horizontal orbital shaking reaction in the
presence of 0.026e0.027 g NiMo/g-Al
2
O
3
catalyst, as shown in
Fig. 5a. Methane is formed from the three hydrogenation reactions,
as shown in Equations (1) through (3), where each reaction
produces 1 mol product and 1 mol CH
4
by consuming 1 mol methyl
laurate. The amount of CH
4
formed from the wrist-action shaking
reaction is expected to be very close to that from the horizontal
orbital shaking reaction, in the case that CH
4
is formed solely from
the three hydrogenation reactions. However, total CH
4
formed from
the wrist-action shaking reaction is higher than that from the
horizontal orbital shaking reaction as shown in Fig. 5b. Unac-
countable and CH
4
formed and hydrogen consumed from the
wrist-action shaking reaction are higher than those from the
horizontal orbital shaking reaction as shown in Fig. 5a and b. These
facts suggest that unaccountable and CH
4
are formed from the
hydrogenation of methyl laurate in the similar way as Equations 1
through 3.
These experimental data on agitating pattern indicate that
hydrodynamics [20] of three-phase mixtures consisting of liquid
reaction mixtures, solid catalyst particles, and gaseous reaction
mixtures in the batch reactor affects signicantly conversion of
methyl laurate as well as distributions of products such as
0
10
20
30
40
50
60
70
80
90
100
110
1 2 3 4 5
L
M
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
methyl_laurate
undecane
dodecane
lauric_acid
unaccountable
0
5
10
15
20
25
30
35
40
45
50
1 2 3 4 5
%
t
h
g
i
e
W
CH4 Production, w
%, basis on initial
biomass
H2 Consumption, w
%, basis on initial
biomass
H2 Consumption,
w %, basis on
initial H2
Amount of Catalyst, g: 1 = 0 2 = 0.026 3 = 0.051 4 = 0.104 5 = 0.126
a b
Fig. 3. Effects of catalyst amount on liquid product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g methyl laurate (ML) with 46.52e47.90 bar initial cold H
2
pressure for 30 min at 350

C.
0
20
40
60
80
100
120
Wrist Action Horizontal
Orbital
Shaking Pattern
L
M
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
undecane
dodecane
lauric_acid
methyl_laurate
unaccountable
0
5
10
15
20
25
30
35
40
45
Wrist Action Horizontal
Orbital
Shaking Pattern
%
t
h
g
i
e
W
CH4
Production, w
%, basis on
initial biomass
H2
Consumption, w
%, basis on
initial biomass
H2
Consumption,
w %, basis on
initial H2
b a
Fig. 4. Effects of shaking pattern on liquid product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g methyl laurate (ML) with 0.1-g catalyst for 30 min at 350

C
and 46.52 bar initial cold H
2
pressure.
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 911
undecane, dodecane, lauric acid, unaccountable, and CH
4
, and
consumption of hydrogen in the presence of 0.026e0.027 g NiMo/
g-Al
2
O
3
catalyst.
3.2. Canola oil
Canola oil (local supermarket) of 2 g is deoxygenated with initial
cold 18.25e85.11 bar hydrogen in the presence of 0.026e0.103 g
NiMo/g-Al
2
O
3
catalyst for 30e60 min at 350e400

C, using a 35-cm
3
batch reactor. Canola oil is converted mainly into heptadecane and
octadecane. Heptadecanic acid is formed as a major intermediate
product.
3.2.1. Temperature
Canola oil of 2 g is deoxygenated with initial cold
46.52e47.21 bar hydrogen in the presence of 0.1 g NiMo/g-Al
2
O
3
catalyst for 30 min at 350e400

C. Formation of heptadecane and
octadecane increases as the reaction temperatures increase,
whereas formation of unaccountable decreases as the reaction
temperatures increase over the temperature range of 350e400

C,
as shown in Fig. 6a.
These experimental data on conversion of canola oil show the
temperature dependence [18] of canola oil conversion. In addition,
this observation suggests that solubility of hydrogen in reaction
mixtures [19] increases with increased temperatures, and increased
concentrations of hydrogen in liquid reaction mixtures result in
increased conversion of canola oil into heptadecane and
octadecane.
3.2.2. Pressure
Canola oil of 2 g is deoxygenated with initial cold
18.25e85.13 bar hydrogen in the presence of 0.1 g NiMo/g-Al
2
O
3
catalyst for 30e60 min at 350

C. Formation of heptadecane and
octadecane, and consumption of H
2
based on the initial canola oil
increase as the initial cold H
2
pressures increase for both the 30-
min reaction duration and the 60-min reaction duration, as shown
in Fig. 7a and b. This observation suggests that solubility of
hydrogen in liquid reaction mixtures [19] increases with increased
pressures, and increased concentration of hydrogen in liquid
reaction mixtures results in increased conversion of canola oil into
heptadecane and octadecane.
Formation of unaccountable products decreases as the initial
cold H
2
pressures increase for both the 30-min reaction duration
and the 60-min reaction duration. These experimental data indi-
cate that elevated hydrogen pressures and prolonged reaction
durations are required to increase conversion of canola oil to
hydrocarbons such as heptadecane and octadecane at 350

C.
3.2.3. Catalyst
Canola oil of 2 g is deoxygenated with initial cold 47.20 bar
hydrogen in the presence of 0.026e0.102 g NiMo/g-Al
2
O
3
catalyst
for 30 min at 350

C. Formation of heptadecane and octadecane
increases as the catalyst amounts increase, whereas formation of
unaccountable products and the intermediate product heptadeca-
noic acid decreases as the catalyst amounts increase, as shown in
Fig. 8a. This observation shows that both catalysts and hydrogen are
needed to convert canola oil to hydrocarbons.
0
20
40
60
80
100
120
Wrist Action Horizontal Orbital
Shaking Pattern
L
M
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
undecane
dodecane
lauric_acid
methyl_laurate
unaccountable
0
2
4
6
8
10
12
14
16
18
20
Wrist Action Horizontal
Orbital
Shaking Pattern
%
t
h
g
i
e
W
CH4
Production, w
%, basis on
initial biomass
H2
Consumption, w
%, basis on
initial biomass
H2
Consumption,
w %, basis on
initial H2
a b
Fig. 5. Effects of shaking pattern on liquid product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g methyl laurate (ML) with 0.026e0.027 g catalyst for 30 min at
350

C and 46.52e47.21 bar initial cold H
2
pressure.
0
10
20
30
40
50
60
70
80
90
100
110
1 2 3
O
C
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
methyl_laurate
hexadecane
heptadecane
octadecane
heptadecanoic_
acid
unaccountable
0
5
10
15
20
25
30
35
40
45
50
1 2 3
%
t
h
g
i
e
W
Gasified
Biomass, w
%, basis on
initial
biomass
H2
Consumption, w
%, basis on
initial
biomass
H2
Consumption,
w %, basis
Reaction Temperature,
o
C: 1= 350 2 =375 3 = 400
b a
Fig. 6. Effects of temperature on liquid product distribution, H
2
consumption, and biomass-generated vapor formation, deoxidizing 2-g Canola oil (CO) with 0.1-g catalyst for 30 min
at 46.52e47.21 bar initial cold H
2
pressure.
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 912
Unaccountable products as well as gaseous products are
signicantly formed from canola oil with initial cold 47.20 bar
hydrogen in the presence of 0.026e0.102 g NiMo/g-Al
2
O
3
catalyst
for 30 min at 350

C, as shown in Fig. 8a and b. Formulation of novel

catalysts, maximum formation of hydrocarbons, minimum forma-
tion of unaccountable and gaseous products, and identication of
reaction conditions suitable for efcient conversion of canola oil to
low-boiling liquid hydrocarbons are essential to bio-reneries
compatible with petroleum reneries.
3.2.4. Agitation of reaction mixtures
Canola oil of 2gis deoxygenatedwithinitial cold45.82e47.20bar
hydrogeninthepresence of 0.1gNiMo/g-Al
2
O
3
catalyst for 30minat
350

C. Formationof heptadecaneandoctadecane, andconsumption

of hydrogen are higher with wrist-action shaking than horizontal
orbital shaking, whereas formation of unaccountable is lower with
wrist-action shaking than horizontal orbital shaking, as shown in
Fig. 9a and b. These experimental data indicate that hydrodynamics
[20] of three-phase mixtures consisting of liquid reaction mixtures,
solid catalyst particles, and gaseous reaction mixtures in the batch
reactor affects signicantly conversion of canola oil as well as
distributions of products such as heptadecane, octadecane, hepta-
decanoic acid, and unaccountable.
4. Conclusions and summary
4.1. Methyl laurate
Methyl laurate is converted mainly to undecane and dodecane in
the presence of hydrogen and NiMo/g-Al
2
O
3
catalyst. Lauric acid is
formed as a major intermediate product. Formation of undecane,
dodecane, and CH
4
increases as catalyst amount increases, whereas
0
20
40
60
80
100
120
18.25 47.21 46.52 85.13
React ion Time 30 min React ion Time 60 min
Initial Cold H
2
Pressure,
Bar
O
C
l
a
i
t
i
n
I
n
o
d
e
s
a
b
,
%
t
h
g
i
e
W
methyl_laurate
pentadecane
heptadecane
octadecane
nonadecane
heptadecanoic
_acid
unaccountable
0
10
20
30
40
50
60
70
80
90
18.25 47.21 46.52 85.13
React ion Time 30
min
React ion Time 60
min
Initial Cold H
2
Pressure, Bar
%
t
h
g
i
e
W
Gasified
Biomass, w
%, basis on
initial biomass
H2
Consumption,
w %, basis on
initial biomass
H2
Consumption,
w %, basis on
initial H2
a b
Fig. 7. Effects of Initial cold H
2
pressure on product distribution, H
2
consumption, and CH
4
formation, deoxidizing 2-g Canola oil (CO) with 0.1-g catalyst for 30e60 min at 350

C.
0
10
20
30
40
50
60
70
80
90
100
110
1 2 3 4
%
w
,
e
r
u
t
x
i
M
t
c
u
d
o
r
P
d
i
u
q
i
L
methyl_laurate
heptadecane
octadecane
heptadecanoic_acid
unaccountable
0
10
20
30
40
50
60
1 2 3 4
%
t
h
g
i
e
W
Gasified Biomass,
w %, basis on
initial biomass
H2 Consumption, w
%, basis on initial
biomass
H2 Consumption,
w %, basis on
initial H2
Amount of Catalyst, g: 1 = 0.026 2 = 0.051 3 = 0.076 4 = 0.102
a b
Fig. 8. Effects of catalyst amount on liquid product distribution, H
2
consumption, and biomass-generated gas formation, deoxidizing 2-g Canola oil (CO) with 45.82e47.21 bar initial
cold H
2
pressure for 30 min at 350

C.
K.C. Kwon et al. / Renewable Energy 36 (2011) 907e915 913
formation of unaccountable products decreases as catalyst amount
increases. Both catalysts and hydrogen are needed for the conversion
of methyl laurate to hydrocarbons such as undecane and dodecane.
Formation of undecane, dodecane, and CH
4
increases as H
2
pressure increases, while formation of unaccountable products
decreases as H
2
pressure increases. Formation of undecane,
dodecane, and CH
4
increase as reaction temperature increases over
the temperature range of 300e350

C, whereas formation of
undecane, dodecane, and CH
4
decreases as reaction temperature
increases over the temperature range of 350e375

C. Unaccount-
able products and gases formed fromliquid methyl laurate increase
as reaction temperatures increase, whereas the intermediate
product lauric acid decreases as reaction temperatures increase.
Liquid reaction mixtures of methyl laurate are increasingly
polymerized so as to increase formation of unaccountable as
reaction temperature increases. Liquid reaction mixtures are cata-
lytically and thermally cracked in the presence of NiMo/g-Al
2
O
3
catalyst and hydrogen so as to increase formation of gaseous
products generated from liquid reaction mixtures as reaction
temperatures increase.
Formation of undecane, dodecane, and CH
4
is higher with wrist-
action shaking than horizontal orbital shaking. However, formation
of lauric acid as an intermediate product is lower with wrist-action
shaking than horizontal orbital shaking. Hydrodynamics of three-
phase mixtures consisting of liquid reaction mixtures, solid catalyst
particles, and gaseous reaction mixtures in the batch reactor affects
signicantly conversion of methyl laurate as well as distributions of
reaction products such as undecane, dodecane, lauric acid, unac-
countable, and CH
4
.
4.2. Canola oil
Canola oil is converted mainly into heptadecane and octadecane
in the presence of hydrogen and NiMo/g-Al
2
O
3
catalyst. Heptade-
canic acid is formed as a major intermediate product. Formation of
heptadecane, octadecane, and heptadecanic acid increases as
amounts of NiMo/g-Al
2
O
3
catalyst increase, whereas formation of
unaccountable products decreases as amounts of the catalyst
increase. Both catalysts and hydrogen are needed to convert canola
oil to hydrocarbons.
Formation of heptadecane, octadecane, and gaseous products
from canola oil increases as reaction temperatures increase. Forma-
tion of unaccountable products decreases as reaction temperatures
increase. Formation of heptadecane and octadecane, and consump-
tion of H
2
increase as H
2
pressure increases, whereas formation of
unaccountable products decreases as H
2
pressure increases. Elevated
hydrogenpressures and prolonged reaction durations are required in
the presence of a catalyst to increase conversion of canola oil to
hydrocarbons such as heptadecane and octadecane.
Formation of heptadecane and octadecane, and consumption of
hydrogen are higher with wrist-action shaking than horizontal
orbital shaking, whereas formation of unaccountable and hepta-
decanic acid as an intermediate product is lower with wrist-action
shaking than horizontal orbital shaking. Hydrodynamics of three-
phase mixtures consisting of liquid reaction mixtures, solid catalyst
particles, and gaseous reaction mixtures in the batch reactor affects
signicantly conversion of canola oil and distributions of reaction
products such as heptadecane, octadecane, heptadecanoic acid, and
unaccountable.
Acknowledgements
The authors would like to thank the U.S. Air Force for supporting
this research project
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Wrist
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Orbital
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O
C
l
a
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