Applied Catalysis A: General 382 (2010) 176180

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Applied Catalysis A: General
j our nal homepage: www. el sevi er . com/ l ocat e/ apcat a
Hydrodeoxygenation of oleic acid and canola oil over alumina-supported
metal nitrides
Jacques Monnier
a,
, Hardi Sulimma
b
, Ajay Dalai
b
, Gianni Caravaggio
a
a
CanmetENERGY, Natural Resources Canada, Ottawa, Ontario K1A 1M1, Canada
b
Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E9, Canada
a r t i c l e i n f o
Article history:
Received 10 December 2009
Received in revised form 15 April 2010
Accepted 17 April 2010
Available online 24 April 2010
Keywords:
Hydrodeoxygenation
Metal nitrides
Molybdenum nitride
Vanadium nitride
Tungsten nitride
Canola oil
Oleic acid
Biomass hydrodeoxygenation
Renewable diesel fuel
a b s t r a c t
Nitrides of molybdenum, tungsten and vanadiumsupported on -Al
2
O
3
were prepared by temperature-
programmed reaction with NH
3
and tested as catalysts for hydrodeoxygenation of oleic acid and canola
oil at 380410

C and 7.15MPa H
2
. The molybdenumnitride catalyst was found superior to the vanadium
and tungsten nitrides for catalytic hydrotreating of oleic acid in terms of fatty acid conversion, oxygen
removal and production of normal alkanes (diesel fuel cetane enhancers). The supported molybdenum
nitride favoured the hydrodeoxygenation of oleic acid to n-C
18
H
38
three times out of four compared to
decarbonylation and decarboxylation. A 450-h long hydrotreating test performed at 400

C and 8.35MPa
H
2
with Mo
2
N/Al
2
O
3
and canola oil, indicated that oxygen removal exceeded 90% over the duration of
the experiment and that the yield of middle distillate hydrocarbons (diesel fuel) ranged between 38 and
48wt% (based on liquid feed).
Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.
1. Introduction
Renewable high-cetane diesel fuels and diesel blending stocks
can be produced by catalytic hydrotreating of vegetable oils, ani-
mal fats and waste restaurant greases over supported transition
metal sulphide catalysts [16]. During catalytic hydrotreating, the
triglycerides andfree fatty acids inthese oils andgreases are deoxy-
genated and converted into straight-chain hydrocarbons (normal
alkanes) with mostly 1518 carbon atoms. These normal alkanes
have superior ignition quality in diesel engines as indicated by
cetane numbers of 95 or higher [7]. These biomass-derived hydro-
carbons can therefore be used as blending stocks to increase the
ignition quality of off-specication middle distillates (diesel fuels)
fromfossil sources and reduce the diesel engine exhaust emissions
of CO, particulate matter (PM), hydrocarbons and NOx [8].
Non-sulphided catalysts are of interest for the production of
renewable transportation fuels from biomass because they elim-
inate the need to add a sulphur compound to a biomass-derived
feedstock in order to prevent the deactivation of sulphided metal
catalysts. Molybdenum, tungsten and vanadium nitride catalysts

Corresponding author. Tel.: +1 613 995 1631; fax: +1 613 996 9400.
E-mail address: jmonnier@nrcan.gc.ca (J. Monnier).
have successfully been tested for removing S from thiophene and
benzothiophene, and removing nitrogen fromquinoline, carbazole
and indole [916]. Oxygen removal by transition metal nitrides
was studied by Ramanathan and Oyama using a model liquid
feed mixture containing dibenzothiophene, quinoline, benzofu-
ran and tetralin in aromatics and alkanes [17]. These experiments
indicated that vanadium nitride (VN) exhibited excellent activity
and selectivity for hydrodeoxygenation of benzofuran. Claridge et
al. performed an extensive study on the synthesis of transition
metal carbide and nitride catalysts from oxide precursors [18].
In the present work, alumina-supported nitrides of molybdenum,
tungsten and vanadium supported on alumina are evaluated for
hydrodeoxygenation of oleic acid and canola oil in terms of prod-
uct yield, oxygen removal and production of diesel fuel cetane
enhancers (normal alkanes). Results of a 450-h long-duration test
assessing the most promising nitride catalyst are also presented.
2. Experimental
2.1. Catalyst preparation
Metal nitride catalysts supported on -Al
2
O
3
were prepared
in a multiple-step process described in this section. The rst
step involved loading molybdenum, tungsten or vanadium on the
0926-860X/$ see front matter. Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.04.035
J. Monnier et al. / Applied Catalysis A: General 382 (2010) 176180 177
support by impregnating -Al
2
O
3
particles (Alfa-Aesar #43855
extrudates crushed to 2040mesh size) by incipient wetness
usingaqueous solutions of ammoniumparamolybdate, ammonium
tungstate or ammoniummetavanadate in deionized water in order
to have the same number of moles of metal nitride on the catalyst
support (basis of 10wt% Mo). The impregnated support was then
dried in air at 110

C and calcined at 500

C for 6h to form-Al
2
O
3
-
supported MoO
3
, WO
3
or V
2
O
5
as determined by X-ray diffraction.
In the next step carried out at atmospheric pressure in a quartz
tubular reactor, conversion of MoO
3
, WO
3
or V
2
O
5
to metal nitride
(Mo
2
N, WNor VN) was achievedby passing pure ammonia over the
catalyst bed 1375h
1
GHSV while rising reactor temperature at a
rate of 1

C/min to 200

C (held constant for 2h), then up to 700

C
(for 5h). After nitriding, the catalyst bed was cooled down in nitro-
gen. Catalysts were passivated in situ at 25

C using a mixture of 1%
O
2
in nitrogen in order to form a thin oxide layer on the catalyst
surface to prevent extensive oxidation of the metal nitrides during
transfer to the automated microreactor systemused for evaluating
their catalytic performance. The supported metal nitride catalysts
had similar surface areas (between 186 and 198m
2
/g), similar pore
volumes (between0.478and0.555cm
3
/g) andsimilar average pore
diameters (between 10 and 11.2nm) based on nitrogen BET analy-
sis.
2.2. Evaluation of catalyst performance
The -Al
2
O
3
-supported nitrides of molybdenum, tungsten and
vanadium were tested for hydrodeoxygenation of oleic acid and
canola oil using a continuous owmicroreactor systemcomprising
a stainless steel 39.5-cm long tubular reactor (6mm ID). A ther-
mocouple placed inside a 1.7-mm OD thermowell measured the
internal temperature of the catalyst bed. The reactor volume was
approximately 10cm
3
. An electric furnace with two 15-cm long
heating zones supplied heat to the reactor. For a fair compari-
son between metal nitrides, the weight of catalyst in the reactor
was adjusted in order to have the same number of moles of
metal nitride in the catalyst bed: 2g 8.2%Mo
2
N/-Al
2
O
3
, 1.26g
4.1%VN/-Al
2
O
3
and 1.42g 11.0%WN/-Al
2
O
3
. The catalyst beds
which were diluted with inert silicon carbide (2040mesh size
particles; 2:1 catalyst to diluent volume ratio), were positioned
at the centre of the electric furnace between two layers of quartz
chips.
Oleic acid (C
17
H
33
COOH) and canola oil were used as feed-
stocks for these hydrodeoxygenation tests. A BeckmanCoulter
high-pressure liquid chromatography pump (System Gold Model
118 Solvent Module) delivered accurate volumes of liquid feeds.
Brooks Smart 5850S mass ow controller delivered a certied
blend of 90% hydrogen and 10% argon supplied by BOC Gases
which was mixed with the liquid feed prior to entering at the
bottom of the reactor. Argon was used as an inert tracer in
order to monitor and correct for any discrepancies in the outlet
gas ow measurements. The upow mode of reactor operation
was selected in order to create a uniform ow distribution and
prevent channelling in the reactor. Two gasliquid separators
were placed in series after the tubular reactor in order to col-
lect most of the liquid products at room temperature and any
condensable products including water at 5

C. Outlet gases were

analyzed on-line using a HP 5890 Series II gas chromatograph.
Process parameters such as pressure, temperature, gas and liq-
uid ow rates, were continuously monitored and recorded by an
automated data acquisition system using National Instruments
FieldPoint
TM
programmableautomationcontrollers andLookout
TM
software.
Hydrotreating tests were performed at temperatures between
380and410

CandH
2
pressureof 7.15MPa. Prior tostartingaseries
of tests with a new catalyst, the passivated layer of metal oxides
was reduced in situ by a 3-h H
2
treatment at 360

C, 200kPa and
1850h
1
GHSV.
2.3. Characterization of liquid products
The liquid products consisted of two immiscible phases (aque-
ous andorganic). Bothliquidphases wereweighedfor mass balance
and yield calculations. The liquid organic products were character-
ized by elemental analysis [contents in carbon, hydrogen, nitrogen,
sulphur and oxygen (by difference)] and by simulated distillation
(ASTM D2887) in order to obtain the boiling point distributions
which were used for calculating the yields of middle distillates
(diesel fuels). The concentrations of unconverted fatty acids were
derived from gas chromatographymass spectrometry (GCMS)
data after methylation of the carboxylic acid groups present in the
liquid organic products. GCMS was preferred to GC-FID for these
characterizations due to the positive identication of all compo-
nents by both their retention time and their mass fragmentation
pattern. The carboxylic acids were methylated using the follow-
ing procedure. The sample (50mg) was weighed in a test tube
(11mm ID105mm) and BF
3
/MeOH (1ml, 14%, wt/wt), toluene
(1ml), and methanol (1ml) were added. The solution was spiked
with deuterated hexadecanoic acid (50l of a 2.5mg/ml solution
inhexane, used as a derivatizationsurrogate check) and deuterated
hexacosane (100l of a 10mg/ml solution, used for the n-alkane
recovery surrogate). The tube was ushed with ultra high purity
nitrogen (to reduce the risk of oxidizing the unsaturated fatty
acids), was capped tightly with a Teon cap and put into a heat-
ing block (preheated to 100

C) for 1h. The mixture was shaken

every 10min to ensure complete mixing. The tube was left to cool
to room temperature. Deionized water (5ml) and hexane (1ml)
were added to the solution and the tube was capped and shaken
for about 1min. The hexane portion (containing the FAMEs) was
transferred using a Pasteur pipette into another test tube contain-
ing 1g of sodiumsulphate to remove water. The driedhexane was
transferredinto a 10-ml volumetric ask. More hexane (2ml) was
added to the initial mixture and the same procedure was repeated
until the volumetric ask was lled. The solution was diluted 20
times for n-alkane analysis, and analyzed as is for the FAME analy-
sis.
The concentrations of normal alkanes were also determined by
GCMS analysis. The GCMS parameters for the analysis of the
fatty acid methyl esters (FAME) and alkanes are shown below. The
hydrogen consumption was estimated from mass balance and ele-
mental analysis.
Quality control included daily calibration curves to ensure that
the quantitationof the compounds was not affectedby variations in
their response factors due to the MS detector or any other variables.
Furthermore, control samples and repeat analyses were used to
check the data.
2.4. GCMS parameters for FAME analysis
GCMS analyses were done with an Agilent 6890 GC equipped
with an autosampler, a 5972A quadrupole mass selective detec-
tor operated in electron impact mode (electron energy 70eV,
ion source temperature 250

C) and a programmable temperature

vaporizing injector (PTV). The chromatography was done with a
Supelco SP-2380 column (0.20m lm, 0.25mm ID, 30m) using
the following conditions: column ow: 1.5ml/min; oven tempera-
ture program: initial temperature: 50

C, nal temperature: 250

C
with a ramp of 3

C/min. The PTV conditions were: initial temper-

ature 70

C, nal temperature 275

C with a ramp of 720

C/min.
The analyses were carried out either in selective ion mode for
quantitative analysis (m/z: 74 and 87 for unsaturated and mono
unsaturated FAMEs, 81 and 95 for double and 79 and 95 for triple
178 J. Monnier et al. / Applied Catalysis A: General 382 (2010) 176180
unsaturated FAMEs) or in scan mode (total ion count, mass range
40550) for identication of compounds. FAMEs were identied
either by comparisonwithretentiontimes of reference compounds
and/or with the help of their MS fragmentation patterns using
the National Institute of Standards and Technology NIST02 library
database software. MS data and chromatograms were recorded
using the Chemstation software.
2.5. GCMS parameters for n-alkane analysis
GC/MS analyses were done with an Agilent 6890 GC equipped
with an autosampler, a 5973 quadrupole mass selective detec-
tor operated in electron impact mode (electron energy 70eV, ion
source temperature 250

C) anda split/splitless injector operatedin

splitless mode at 275

C. The chromatography was done with a DB-

5MS, fused silica capillary column (0.25mlm, 0.25mmID, 30m)
using the following conditions: columnow: 1.5ml/min, inlet tem-
perature: 275

C, temperature program: initial temperature: 50

C,
temperature #1: 280

C with a ramp of 4

C/min, nal temperature:

320

C with a ramp rate of 6

C/min. The analyses were carried out

either in selective ion mode for quantitative analysis (m/z: 85 for
n-alkanes and 66 for deuterated hexacosane) or in scan mode (total
ioncount, mass range 40550) for identicationof compounds. The
normal alkanes were identied using the same approach as the
FAMES as described above.
3. Results and discussion
3.1. Hydrodeoxygenation of oleic acid
In hydrotreating experiments using oleic acid (C
17
H
33
COOH) as
feedstock, the performances of nitrides of molybdenum, tungsten
and vanadium supported on -Al
2
O
3
were compared in terms of
conversion of oleic acid, oxygen removal, product yield, concentra-
tion of normal alkanes in the liquid products and composition of
gaseous products. The conversion of oleic acid was calculated from
GCMS data.
Table 1 presents a summary of the experimental results
obtained from hydrotreating oleic acid with these catalysts at
380

C, 7.15MPa H
2
, 0.45h
1
liquid hourly space velocity (LHSV)
and 810L H
2
/L oleic acid feed ratio. In order to have steady-state
conditions, the catalysts were on-stream for a minimum period of
40hbefore taking the product samples presentedinTable 1. Ineach
case, the liquid samples were collected for at least 20h at steady
state to generate enough products for characterization. Conversion
of oleic acid exceeded 97.0% over all catalysts based on residual
acid content in the liquid organic products. Yields of liquid organ-
ics were the highest with molybdenum and vanadium nitrides
(8485g/100g oleic acid) and the lowest with tungsten nitride
(81g/100g C
17
H
33
COOH). Characterization of the liquid organic
products by elemental analysis conrms that oxygen removal is
almost complete over the molybdenum and tungsten nitride cat-
alysts. On the other hand, with the vanadium nitride catalyst,
deoxygenation is lower at about 72% due to the presence of oxy-
genated intermediate compounds, such as ketones and aldehydes,
in the liquid products.
As shown in the following reactions, oxygen can be removed
from oleic acid (C
17
H
33
COOH) as water by hydrodeoxygenation
(reaction (1)), as CO and H
2
O by hydrodecarbonylation (reaction
(2)) or as CO
2
by hydrodecarboxylation (reaction (3)):
4H
2
+C
17
H
33
COOH n-C
18
H
38
+2H
2
O (1)
2H
2
+C
17
H
33
COOH n-C
17
H
36
+CO + H
2
O (2)
1H
2
+C
17
H
33
COOH n-C
17
H
36
+CO
2
(3)
Table 1 indicates that the highest yield of water was obtained
with molybdenum nitride, reaching 9.7g H
2
O/100g C
17
H
33
COOH.
On the other hand, with vanadium nitride, very little water was
formed (2.4g H
2
O/100g C
17
H
33
COOH) but the combined yields
of CO and CO
2
(4.2g/100g C
17
H
33
COOH) were almost twice as
highas those achievedwithMo
2
N(about 2.2g/100g C
17
H
33
COOH),
at similar oleic acid conversions and substantial oxygen removal
(about 72% for VN). These are clear indications that both hydrode-
carbonylation (reaction (2)) and hydrodecarboxylation (reaction
(3)) are signicant reactions with the vanadium nitride catalyst.
Over tungstennitride, hydrodecarbonylationandhydrodecarboxy-
lation reactions are also important (similar combined yields of CO
and CO
2
as those obtained with V nitride) but due to higher oxy-
gen removal (100%) and enhanced hydrodeoxygenation (reaction
(1)), the production of water increased signicantly: up to 4.2g
H
2
O/100g C
17
H
33
COOH.
Table 2 gives the composition of the reactor outlet gases in
terms of H
2
, CO, CO
2
, light hydrocarbons and H
2
O. Using a process
simulation software (Simulated Sciences PRO/II), we calculated the
thermodynamic equilibrium of the water gas shift (WGS) reaction
at 380

C and 8.3MPa, starting with the concentrations of CO, CO

2
,
H
2
OandH
2
measuredat thereactor outlet. Wefoundthat theactual
outlet concentrations of CO, CO
2
, H
2
O and H
2
are very close to the
WGS thermodynamic equilibrium for molybdenum and tungsten
catalysts. These ndings obtained with Mo
2
N and WN are in line
with those reported by several authors indicating that molybde-
num and tungsten carbides are good WGS catalysts [19,20]. In the
case of the vanadiumnitride catalyst, the measured outlet concen-
trations of CO, CO
2
, H
2
Oand H
2
are not at equilibrium. As shown in
Table 2, a change in CO and CO
2
concentrations of more than 30%
is necessary to reach equilibrium. This is achievable by the reverse
water gas shift reaction (CO
2
+H
2
H
2
O+CO).
In Fig. 1, the performances of nitrides of molybdenum, tung-
sten and vanadium supported on -Al
2
O
3
are compared in terms
of distribution of normal alkanes in the liquid organic products,
based on GCMS data. Normal alkanes boiling in the diesel fuel
range can provide superior ignition quality (high-cetane number)
Table 1
Comparing the performance of metal nitride catalysts supported on -Al
2
O
3
for catalytic hydrotreating of oleic acid at 380

C, 7.15MPa H
2
, 0.45h
1
and 810L H
2
/L oleic acid.
Molybdenum nitride Tungsten nitride Vanadium nitride
Conversion of oleic acid (%) 99.9 97.1 97.0
Oxygen removal (%) 100 100 71.8
Product yields (g/100 g oleic acid)
Liquid organic products 84.1 81.1 85.0
CH
4
0.160 0.101 0.113
C
2
H
6
0.356 0.194 0.184
CO 0.613 1.56 1.63
CO
2
1.59 2.22 2.55
Water 9.7 4.2 2.4
n-C
17
/(n-C
17
+n-C
18
) molar ratio in liquid products 0.24 0.67 0.85
J. Monnier et al. / Applied Catalysis A: General 382 (2010) 176180 179
Table 2
Process simulation data (in mol%) for calculating water gas shift equilibrium at 380

C and 8.3MPa.
Mo
2
N/-A1
2
O
3
WN/-Al
2
O
3
VN/-Al
2
O
3
Reactor outlet WGS equilibrium Reactor outlet WGS equilibrium Reactor outlet WGS equilibrium
CO 0.58 0.45 1.41 1.38 1.37 1.78
CO
2
0.95 1.08 1.28 1.30 1.37 0.96
H
2
83.72 83.85 91.06 91.08 93.85 93.45
H
2
O 14.18 14.05 5.93 5.91 3.10 3.50
Hydrocarbons 0.57 0.57 0.32 0.32 0.31 0.31
Fig. 1. Concentration of n-alkanes in the liquid organic products from catalytic
hydrotreating of oleic acid over supported metal nitrides at 380

C, 0.45h
1
,
7.15MPa H
2
and 810L H
2
/L oleic acid feed ratio.
to diesel fuels, resulting in lower diesel exhaust emissions of regu-
latedpollutants [8]. Hence, as the carbonnumber of normal alkanes
increases from 9 to 15, the cetane number (ignition quality) rises
clearly above commercial diesel fuel specications from 72 to 95
[7]. GCMS characterizationof the liquidorganic products indicates
that over the supported Mo
2
Ncatalyst, normal alkanes account for
about 30wt% of the liquid organic products, corresponding to more
than three times the n-alkane contents obtained with nitrided V
and W catalysts (10wt% or less).
The following major n-alkanes were identied in the liquid
organic products: n-octadecane (n-C
18
H
38
), n-decane (n-C
10
H
22
),
n-heptadecane (n-C
17
H
36
), n-nonane (n-C
9
H
20
) and n-undecane
(n-C
11
H
24
). Normal octadecane was formed by hydrodeoxy-
genation (reaction (1)), n-heptadecane, by hydrodecarbonylation
(reaction (2)) and hydrodecarboxylation (reaction (3)), n-nonane
and n-decane, by subsequent carbon-carbon bond breaking at the
olenic bond of the fatty acid or next to it. The GCMS data show
that beyond C18, very little normal alkanes are formed. Normal
nonadecane is about 20 times smaller than n-octadecane, and
n-eicosane (n-C
20
H
42
), about 40 times smaller. The only excep-
tion is n-hexacosane (n-C
26
H
54
) which is relatively high (but still
10 times smaller than n-octadecane). This is most likely due to
recombination of adsorbed C17 and C9 fragments. The supported
molybdenum nitride catalyst produced 8 times more octadecane
than tungsten and vanadiumnitride catalysts, thus conrming that
Mo
2
N has better HDO and hydrogenation activities. In addition,
Mo
2
Nproduced three times more n-C
9
H
20
, n-C
10
H
22
and n-C
11
H
24
combined than other catalysts, indicating very good hydrogenol-
ysis activity. The molar ratio of n-C
17
/(n-C
17
+n-C
18
) in the liquid
products presented in Table 1 indicates that molybdenum nitride
favours the hydrodeoxygenation of oleic acid to n-C
18
H
38
three
times out of four compared to decarbonylation and decarboxyla-
tion. In the case of the supported vanadium nitride catalyst, oleic
acid was mostly deoxygenated by decarbonylation and decarboxy-
lation based on a n-C
17
/(n-C
17
+n-C
18
) ratio of 0.85. The tungsten
nitride catalyst was in-between.
Hydrogen consumption is also an indication of the level of cat-
alytic activity in terms of hydrodeoxygenation (reaction (1)). In
the case of Mo
2
N tested between 380 and 410

C, H
2
consumption
ranged between 165 and 185L H
2
/L C
17
H
33
COOH. These values are
the highest recorded in this comparative study. They are consistent
with other results obtained with molybdenumnitride such as oleic
acid conversion, oxygen removal, and n-alkane content in the liq-
uid organic products. Hydrogen consumption is less than 100L/L
C
17
H
33
COOH for supported W nitride. In the case of supported
vanadiumnitride, lower oxygen removal (72%) combined with sig-
nicant decarbonylation and decarboxylation activity (forming CO
and CO
2
instead of H
2
O), would explain why H
2
consumption was
below 50L/L C
17
H
33
COOH.
3.2. Long-duration performance test with canola oil
Due to its superior performance among metal nitrides in terms
of oxygen removal, oleic acid conversion and yield of normal alka-
nes, the supported molybdenumnitride was selected as catalyst for
hydrotreating canola oil, a triglyceride feedstock whichis produced
in large volumes in Western Canada. The 450-h long-duration
test was performed at 400

C, 8.3MPa H
2
, 0.9h
1
LHSV and 810L
H
2
/L canola oil feed ratio. The time-on-stream performance of
27%Mo
2
N/-Al
2
O
3
was evaluated during these 450h in terms of
yield of middle distillates (dened as the 155325

C fraction of
the liquidorganic products). Fig. 2indicates that the performance of
the Mo
2
N/-Al
2
O
3
catalyst was fairly stable over 450h of continu-
ous operation. Oxygen removal exceeded 90% and remained steady
during the test. The yield of middle distillates reached 48g/100g
canola oil at rst but declined with time to 38g/100g canola after
450h on stream. The yield of heavier hydrocarbons (fraction of
liquid organic products boiling above 325

C) increased with time

but did not exceed 32.8g/100g canola oil. The yield of naphtha
(IBP155

C boiling point range) decreased from 7.1 to 5.2g/100g

canola oil.
Fig. 2. Yield of middle distillates (155325

C) as a function of time-on-stream in
catalytic hydrotreating of canola oil over 27%Mo
2
N/-Al
2
O
3
at 400

C, 8.3MPa H
2
,
0.9h
1
LHSV and 810L H
2
/L canola oil feed ratio.
180 J. Monnier et al. / Applied Catalysis A: General 382 (2010) 176180
Commercial hydrotreating catalysts, which are typically sul-
phided nickelmolybdenum or cobaltmolybdenum catalysts
supported on -Al
2
O
3
, have been used for hydrodeoxygenation of
vegetable oils to hydrocarbons in the diesel fuel boiling range [1,4].
Inour work, we foundthat oxygenremoval fromcanola oil at 380

C
and 8.3MPa reached almost 100% with a commercial sulphided
nickelmolybdenum catalyst (13wt% Mo, 3wt% Ni), which is
slightly better than for supported molybdenumnitride (90%). The
most signicant difference in performance between the nitrided
Mo catalyst and the commercial sulphided Mo catalyst is in the
product distribution. Higher yields of middle distillates (targeted
product) were obtained with the commercial catalyst (80g/100g
canola oil versus less than 50g/100g canola oil for the nitrided
Mo catalyst) and lower yields of undesirable +325

C hydrocarbons
(less than 5g/100g canola oil compared to more than 27g/100g
canola oil for the Mo
2
N catalyst). This is most likely due to the
higher hydrogenation capability of the commercial hydrotreating
catalyst.
3.3. Thermodynamics of reactions of metal nitrides
It is possible to have an indication of the stability of metal
nitrides (Mo
2
N, VNor WN) using thermodynamic calculations [21].
For the following reactions:
1Mo
2
N + 3/2H
2
= 2Mo + 1NH
3
(4)
1VN + 3/2H
2
= 1V + 1NH
3
(5)
the equilibrium constant K [corresponding to the ratio of (par-
tial pressure of NH
3
)/(partial pressure of H
2
)
3/2
] can be estimated
using thermodynamic data [22]. These calculations indicate that
in the temperature range of 327427

C, the equilibrium constant

K for the Mo
2
N reduction increases from 0.00014 (at 327

C) to
0.00029 (at 427

C) and that for VN, from 1.8510

16
(327

C) to
2.0210
14
(427

C). Based on these numbers, Mo

2
N is not as sta-
ble as VN and can potentially be reduced if the partial pressure of
ammonia is very low.
In the case of the following oxidation reaction involving
Mo
2
N:
1Mo
2
N + 4H
2
O = 2MoO
2
+1NH
3
+5/2H
2
(6)
the equilibrium constant K is dened as the following ratio:
[Partial pressure of NH
3
] [Partial pressure of H
2
]
5/2
[Partial pressure of H
2
O]
4
The value of K drops from 49,890 (at 327

C) to 450 (at 427

C),
indicating that oxidation of Mo
2
Nis possible at these reaction con-
ditions. However, very high partial pressure of hydrogen would
prevent oxidation of Mo
2
N.
In the case of VN oxidation:
1VN + 1H
2
+1H
2
O = 1VO + 1NH
3
+1/2H
2
(7)
the equilibrium constant K is equal to:
[Partial pressure of NH
3
] [Partial pressure of H
2
]
1/2
[Partial pressure of H
2
][Partial pressure of H
2
O]
The equilibrium constant K decreases from 0.030 (at 327

C) to
0.017 (at 427

C). Thus, VN is signicantly more stable than Mo

2
N,
but oxidation is still possible. As in the case of Mo
2
N, charac-
terization of the used VN catalyst would give a more accurate
answer on chemical changes affecting the metal nitride active
sites.
4. Conclusions
The molybdenum nitride catalysts supported on -Al
2
O
3
have
shown superior performances for the hydrodeoxygenation of oleic
acid compared to supported nitrides of tungsten and vanadium
in terms of oleic acid conversion (almost 100% at 380

C and
8.35MPa H
2
), oxygen removal (100%) and higher production of
normal alkanes (excellent diesel fuel cetane enhancers). Experi-
mental results indicate that Mo
2
Nfavours the hydrodeoxygenation
three times out of four for the removal of oxygen from oleic acid
over hydrodecarbonylation and hydrodecarboxylation. In the case
of the supported vanadium nitride catalyst, oleic acid was mostly
deoxygenated by decarbonylation and decarboxylation. A 450-h
hydrotreating test performed with Mo
2
N/-Al
2
O
3
and canola oil
as feedstock indicated high oxygen removal throughout the test
(exceeding 90%). Improvements are nevertheless required in terms
of product distribution in order to maximize the yield of high-
cetane middle distillates (diesel fuel range hydrocarbons).
Acknowledgements
The authors wouldlike tothankMr. Bruce Dick, Mr. Luc Pelletier,
Mr. Guy Tourigny and the staff of the Characterization Laboratories
of CanmetENERGY, Natural Resources Canada, for technical assis-
tance. Financial support of the Natural Sciences and Engineering
Research Council of Canada and the Federal Program on Energy
Research and Development (PERD) of Natural Resources Canada is
gratefully acknowledged.
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