Bio-diesel production from deoxygenation reaction over Ce0.6Zr0.4O2 supported transition metal (Ni, Cu, Co, and Mo) catalysts

Article abstract of DOI:10.1166/jnn.2016.10987

Ce_0.6Zr_0.4O₂ supported transition metal (Me = Ni, Cu, Co, and Mo) catalysts have been investigated to screen for the catalytic activity and selectivity for deoxygenation reaction of oleic acid. Me - Ce_0.6Zr_0.4O₂ catalysts were prepared by a co-precipitation method. Ni - Ce_0.6Zr_0.4O₂ catalyst exhibited much higher oleic acid conversion, selectivity for C₉ to C₁₇ compounds, and oxygen removal efficiency than the others. This is mainly ascribed to the presence of free Ni species, synergy effects between Ni and Ce_0.6Zr_0.4O₂, and the highest BET surface area.

Full text of DOI:10.1166/jnn.2016.10987

Article
Journal of
Nanoscience and Nanotechnology
Vol. 16, 4587–4592, 2016
Copyright © 2016 American Scientific Publishers
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Printed in the United States of America
Bio-Diesel Production from Deoxygenation Reaction
Over Ce0ꢀ6Zr0ꢀ4O2 Supported Transition Metal
(Ni, Cu, Co, and Mo) Catalysts
Jae-Oh Shim1, Dae-Woon Jeong1, Won-Jun Jang1, Kyung-Won Jeon1,
Byong-Hun Jeon1, Seong-Heon Kim1, Hyun-Seog Roh1ꢀ∗, Jeong-Geol Na2,
Sang Sup Han3, and Chang Hyun Ko4ꢀ∗
1Department of Environmental Engineering, Yonsei University, 1 Yonseidae-Gil, Wonju, Gangwon, 220-710, S. Korea
2Biomass and Waste Energy Laboratory, Korea Institute of Energy Research (KIER), Daejeon, 305-343, S. Korea
3Petroleum and Gas Research Center, Korea Institute of Energy Research (KIER), Daejeon, 305-343, S. Korea
4School of Applied Chemical Engineering, Chonnam National University, 77 Yongbong-ro,
Buk-Gu, Gwangju, 500-757, S. Korea
Ce0ꢀ6Zr0ꢀ4O2 supported transition metal (Me = Ni, Cu, Co, and Mo) catalysts have been investigated
to screen for the catalytic activity and selectivity for deoxygenation reaction of oleic acid. Me–
Ce0ꢀ6Zr0ꢀ4O2 catalysts were prepared by a co-precipitation method. Ni–Ce Zr0ꢀ4
O catalyst exhib-
Delivered by Ingenta to: Nanyang Technological Un0ivꢀ6ersity2
ited much higher oleic acid conversion, selectivity for C to C compounds, and oxygen removal
IP: 5.189.202.183 On: Thu, 09 9Jun 210716 02:53:11
efficiency than the others. This is mainly ascribed to the presence of free Ni species, synergy effects
Copyright: American Scientific Publishers
between Ni and Ce0ꢀ6Zr0ꢀ4O2, and the highest BET surface area.
Keywords: Ce0ꢀ6Zr0ꢀ4O2, Transition Metal, Deoxygenation, Ni, Synergy Effect.
1. INTRODUCTION
to improve its quality. For this reason, the hydrodeoxy-
genation (HDO) process has been developed; however,
this process requires excess hydrogen for the reaction to
occur.6 Thus, deoxygenation (DO) processes can be con-
sidered as an alternative to HDO.
Bio-diesel has received a great deal of attention in
recent years due to its importance as a carbon-neutral
energy source as well as increased demand in trans-
portation fuel market. Biomass can be transformed into
bio-diesel using many kinds of processes: fermenta-
tion, trans-esterification, pyrolysis, gasification with the
Fisher-Tropsch synthesis, and hydrogenation.1 Above all,
the trans-esterification process has been widely used
to produce bio-diesel.2ꢀ3 Trans-esterification is the reac-
tion of triglycerides (RCOOH2−RCOOH–RCOOH2ꢁ with
methanol (CH3OH) to form fatty acid methyl ester (FAME,
3RCOOCH3ꢁ.2ꢀ4 This process can successfully produce
bio-diesel in commercial plants. However, FAME bio-
diesel is not suitable use directly as diesel engine fuel
because it contains a large amount of oxygen and exhibits
poor flow quality at low temperatures.4 In addition, ther-
mal instability, corrosiveness, and low heating value are
caused by the high oxygen content in FAME bio-diesel.5
Accordingly, oxygen must be removed from the bio-diesel
Ni or Co metal oxide promoted molybdenum sulphide
(MoS2ꢁ catalysts and noble metal catalysts are commonly
used for the HDO process.7–9 However, molybdenum sul-
phide based catalysts have significant drawbacks, such as
the fact that they require the use of problematic sulfided
catalysts and high concentrations of hydrogen. Moreover,
conventional transition metal based sulfided catalysts were
found to be quickly deactivated by coke deposition in
HDO reaction and required additional regeneration steps
and equipment.10 Additionally, noble metal catalysts may
cause an increase in process costs because they are rare
and costly.8 Therefore, it is important to develop non-
sulfided and cost-effective catalysts for DO reaction.11–16
Catalyst acidity is known to be important for deoxy-
genation reaction and several recent studies have suggested
that acidity is an important factor in deoxygenation reac-
tion as well.17–20 Wang et al. found that acidity of the
∗Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 5
1533-4880/2016/16/4587/006
doi:10.1166/jnn.2016.10987
4587

Bio-Diesel Production from Deoxygenation Reaction Over Ce0ꢂ6Zr0ꢂ4O2 Supported Transition Metal
Shim et al.
catalyst was essential for the DO reaction of high oxygen
content compounds.17 Also, Zuo et al. reported that the
acidic function of catalysts could mediate product selec-
tivity via controlling decarbonylation and decarboxylation
during the DO reaction.20 However, earlier reports suggest
that the strong acidity of the catalyst was responsible for
the cracking.
and the crystallite size was estimated by using the Scherrer
equation.22–25 Temperature programmed reduction (TPR)
was carried out using an Autochem 2920 (Micromeritics).
NH3-temperature programmed desorption (NH3-TPD) was
performed on an Autochem 2920 (Micromeritics). The
sample of 0.1 ꢀg in a quartz reactor was pretreated with
He gas at 300 C for ꢀ10 min and then cooled down. NH3
was adsorbed at 100 C for 30 min and weakly adsorbed
NH3 was removed by purging with He for 1 h. The sam-
Several recent studies have found that CeO2, ZrO2, and
CeO2−ZrO2 supported transition metal catalysts are active
for HDO or DO reaction. Peng et al. reported that ZrO2
supported Ni catalysts were active for DO of microalgae
ꢀ
ple ꢀwas heated from 100 to 1000 C at a heating rate of
10 C/min in He flow and the desorbed amount of NH3
was detected with a thermal conductivity detector (TCD).
The total desorbed NH3 amount was estimated by inte-
grating the NH3-TPD profile. The detailed procedure for
TPR was described previously.26ꢀ27 Oxygen content was
measured by elementary analysis using Thermo Finnigan
FLASH EA-1112 Elemental Analyzer (EA).
ꢀ
oil at 270 C under 40 bar of pure H2 pressure in both
batch and continuous flow modes.21 Yakovlev et al. found
that CeO2, ZrO2, and Ce–ZrO2 supported Ni–Cu catalysts
were active for HDO of anisole over a wide temperature
ꢀ
range from 280 to 340 C under 20 bar of 50% H2 pres-
sure in continuous flow mode.8 Additionally, Zhang et al.
reported that Ni–Cu/ZrO2–SiO2 catalꢀysts exhibited high
activity for HDO of guaiacol at 300 C under 50 bar of
H2 pressure in batch mode.11 In our previous study, the
Ce0ꢂ6Zr0ꢂ4O2 catalyst exhibited higher oleic acid conversion
and higher C9∼C17 (diesel fuel range) selectivity in DO.6
This is mainly due to easier reducibility and higher oxygen
storage capacity. However, there are still remaining goals
to achieve enhancement of catalytic activity and selectivity
of Ce0ꢂ6Zr0ꢂ4O2 catalyst for DO reaction.
2.3. Catalytic Reaction
The deoxygenation reactions were carried out in an auto-
clave reactor (100 mL) operating in batch mode. Metal
oxides can be reduced to form surface defects, such as
anionic vacancies that can catalyze hydrogenation reac-
tions under typical HDO condition. Thus, all prepared cat-
alysts were reduced in a 10 vol.% H2/Ar stream at 700 ꢀC
for 2 h and then cooled down to room temperature in N2
before the reaction. In a typical batch experiment, 27.5 g
of oleic acid and 0.6875 g of catalyst (reactant/catalyst =
In this study, we have designed Ce0ꢂ6Zr0ꢂ4O2 supported
Delivered by Ingenta to: Nanyang Technological University
transition metal (Ni, Cu, Co, and Mo) catalysts for DO
IP: 5.189.202.183 On: Thu, 09 Jun 2016 02:53:11
reaction. Me–Ce0ꢂ6Zr0ꢂ4O2 catalyst was applied for DO of
40/1, wt/wt) were placed in the reactor. The detailed pro-
cedure for the DO reaction was explained in a previous
paper.6 The liquid products were collected after filtering
out the solid phase catalysts. The liquid products were ana-
lyzed by a gas chromatograph (HP 6890N) equipped with
a flame ionization detector and a capillary column (HP-5,
30 m).
Copyright: American Scientific Publishers
ꢀ
oleic acid in batch mode at 300 C under 1 bar of 20%
H2/N2 condition. The effect of transition metals on the
catalytic performance has been interpreted through char-
acterization of BET, XRD, and TPR, and related to the
performance results in DO.
2. EXPERIMENTAL DETAILS
2.1. Catalyst Preparation
3. RESULTS AND DISCUSSION
Ni–Ce0ꢂ6Zr0ꢂ4O2 (Ni–CZO), Cu–Ce0ꢂ6Zr0ꢂ4O2 (Cu–CZO),
Co–Ce0ꢂ6Zr0ꢂ4O2 (Co–CZO), and Mo–Ce0ꢂ6Zr0ꢂ4O2 (Mo–
CZO) catalysts were prepared by a co-precipitation
method. The Ni, Cu, Co, and Mo loading were fixed
at 20 wt%. Stoichiometric quantities of metal pre-
cursors (Ni(NO3ꢁ2 · 6H2O (97%, Junsei), Cu(NO3ꢁ2 ·
6H2O (99%, Aldrich), Co(NO3ꢁ2 · 6H2O (99%, Aldrich),
(NH4ꢁ6Mo7O24 · 6H2O (98%, Aldrich)), Ce(NO3ꢁ3 · 6H2O
(99%, Aldrich) and zirconyl nitrate solution (20 wt% ZrO2
basis, MEL Chemicals) were combined in distilled water.
The detailed preparation method was described in a previ-
ous paper.6
3.1. Catalyst Characterization
The characteristics of Ce0ꢂ6Zr0ꢂ4O2 (CZO) supported tran-
sition metal catalysts are listed in Table I. The BET surface
area of Ni–CZO is the highest among the prepared cata-
lysts. In contrast, Cu–CZO exhibits the lowest BET sur-
face area. The BET surface area decreases in the following
Table I. Characteristics of Me–CZO catalysts (Me = Ni, Cu, Co, and
Mo).
BET surface
Metal oxide
Reduced metal
Catalyst
areaa (m2/g) crystallite sizeb (nm) crystallite sizeb (nm)
CZO
171
183
121
147
148
–
–
Ni–CZO
Cu–CZO
Co–CZO
Mo–CZO
N. A.c
22.3
12.5
23.4
16.7
N. A.c
2.2. Characterization
16.2
N. A.c
The BET surface area was measured by nitrogen adsorp-
tion at −196 ꢀC using an ASAP 2000 (Micromeritics). The
XRD patterns were recorded using a Rigaku D/MAX–IIIC
diffractometer (Ni filtered Cu–K radiation, 40 kV, 50 mA),
Notes: aEstimated from N2 adsorption at −196 ꢀC; bEstimated from XRD; cNot
available due to very broad and weak XRD peaks.
4588
J. Nanosci. Nanotechnol. 16, 4587–4592, 2016

Shim et al.
Bio-Diesel Production from Deoxygenation Reaction Over Ce0ꢂ6Zr0ꢂ4O2 Supported Transition Metal
order: Ni–CZO > CZO > Mo–CZO > Co–CZO > Cu–
CZO. This result indicates that Ni has the beneficial effect
of increasing the BET surface area of CZO.
Mo-CZO
Co-CZO
The inset of Figure 1 shows diffraction patterns of cal-
cined Me–CZO catalysts. All the catalyst samples exhibit
a cubic structure.28–32 The XRD patterns of calcined CZO
supported Ni and Mo samples do not exhibit the charac-
teristic peaks of metal oxides species. This is due to that
the size of Ni and Mo oxides are beyond the detection
capacity of the powder XRD technique. On the contrary,
Co–CZO and Cu–CZO catalysts show the metal oxide
peaks (Co3O4 and CuO). XRD patterns of the catalysts
after reduction are shown in Figure 1. All catalysts retained
the cubic structure despite reduction at higher tempera-
tures as compared with calcination temperatures. Except
for Mo–CZO, all catalysts show the diffraction peaks of
metallic Ni, Cu, and Co. Table I summarizes the crystal-
lite sizes of metal oxides and reduced metals, calculated
from Scherrer’s equation. The crystallite sizes of MoO3
and NiO cannot be calculated due to very broad and weak
peaks. The crystallite sizes of CuO and Co3O4 are 23.5
and 17.5 nm, respectively. Metallic Cu0 and Co0 crystal-
lite sizes are similar to their respective calcined samples
but slightly increased. Interestingly, metallic Ni0 crystallite
size increases dramatically after Ni–CZO catalyst reduc-
tion. This is due to the relatively high reduction tempera-
ture compared to the calcination temperature.
Cu-CZO
Ni-CZO
200
400
600
800
Temperature (ºC)
Figure 2. TPR patterns of Me–CZO catalysts (Me = Ni, Cu, Co,
and Mo).
species has beneficial effect on decarboxylation of oleic
acid.5 In addition, deoxygenation of fatty acids to hydro-
carbons by the concerted adsorption process of oxide
support surface oxygen defect sites and free Ni oxygen
vacancies.21 For Mo–CZO catalyst, MoO3 and bulk CeO2
peaks are observed at 460 C and 890 C, respectively.35
The Co–CZO catalyst shows one clear peak and one broad
peak. The first clear peak, appearing at 280 ꢀC is attributed
to the reduction of Co3O4.36 The second broad peak is
attributable to the reduction of CoO and bulk CeO2. In
ꢀ
ꢀ
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TPR patterns of Me–CZO catalysts are depicts in
the case of Cu–CZO, two reduction peaks can be seen
IP: 5.189.202.183 On: Thu, 09 Jun 2016 02:53:11
ꢀ
ꢀ
Figure 2. In the case of Ni–CZO, two reduction peaks
Copyright: American Scientific Publishers
around 96 C and 167 C. The first peak can be attributed
to the rꢀeduction of surface CuO species. The second peak
at 167 C is due to the reduction of finely dispersed CuO
species.37 Based on the TPR experiments, we assume that
can be assigned to the reduction of NiO and bulk CeO2.
The first broad reduction peak appears in the tempera-
ꢀ
ꢀ
ture range between 270 C and 660 C. This peak can
be assigned to the reduction of both free Ni and com-
plex Ni species. Complex Ni species have intimate con-
tact with the support.33 The second peak, appearing at
around 830 ꢀC is attributable to the reduction of bulk
CeO2.34 In our previous results, reduction of the free Ni
ꢀ
at a reduction temperature of 700 C, all the metal oxide
samples are in the metallic state.
3.2. Reaction Results
Figure 3 shows oleic acid conversion over Me–CZO cata-
lysts. All catalysts exhibited higher oleic acid conversion
than the blank test. Additionally, Ni–CZO, Cu–CZO, and
MoO
3
Mo-CZO
Co-CZO
Co O
Co O
4
3
3
4
CuOCuO
NiO NiO
100
Cu-CZO
Ni-CZO
89.7
84.7
Mo0
79.6
80
73.8
69.3
Co0
Cu0
Mo-CZO
60
Co-CZO
Cu0
Cu0
43.7
40
Ni0
Ni0
Cu-CZO
20
0
Ni-CZO
20
30
40
50
60
70
80
2θ (degree)
Blank
CZO
Ni-CZO Cu-CZO Co-CZO Mo-CZO
Figure 1. XRD patterns of reduced Me–CZO catalysts. Inset: calcined
Me–CZO catalysts.
Figure 3. Conversion of oleic acid over Me–CZO catalysts (Me = Ni,
Cu, Co, and Mo).
J. Nanosci. Nanotechnol. 16, 4587–4592, 2016
4589

Bio-Diesel Production from Deoxygenation Reaction Over Ce0ꢂ6Zr0ꢂ4O2 Supported Transition Metal
Table II. Oxygen removal efficiency of DO reaction products. Table III. Catalyst acidity and liquid product yield.
Acidity Liquid Gaseous
Shim et al.
Oxygen
Oxygen removal
Liquid
content (%)
efficiency (%)
Catalyst
(ꢃmol•NH /g•cat ꢁ products (g) products (g) yield (%)
3
Oleic acid (reactant)
Blank test
CZO
Ni–CZO
Cu–CZO
11ꢂ5
10ꢂ4
8ꢂ0
5ꢂ9
6ꢂ7
–
9ꢂ6
CZO
824.43
692.15
–
–
13.00
17.57
15.04
10.16
14ꢂ50
9ꢂ93
12ꢂ46
17ꢂ34
47.3
63.9
54.7
36.9
Ni–CZO (3 h)
Ni–CZO (6 h)
Ni–CZO (12 h)
30ꢂ4
48ꢂ3
41ꢂ7
45ꢂ2
25ꢂ9
Co–CZO
Mo–CZO
6ꢂ3
8ꢂ5
the following order: Ni–CZO > CZO > Cu–CZO > Mo–
CZO > Blank > Co–CZO. In the case of Ni–CZO, selec-
tivity for C9∼C17 compounds (27.3%) was approximately
2 times higher than the blank test and 9.2% higher than
CZO. This result indicates that the synergistic effects of
nickel (high selectivity) and CZO (high oleic acid con-
version) have a positive effect on C9∼C17 selectivity.
Additionally, this result is well matched with previously
reported results.39
After reaction, only Ni oxide could enhance both oleic
acid conversion and selectivity for C9∼C17 compounds.
We compared the acidity effects of the cracking reaction
over CZO and Ni–CZO. Table III summarizes the acidity
and product yield of the catalyst. As listed in Table III,
Co–CZO catalysts exhibited higher oleic acid conversion
than CZO catalyst. The oleic acid conversion decreased
in the following order: Ni–CZO > Co–CZO > Cu–CZO >
CZO > Mo–CZO > Blank. These results indicate that oleic
acid conversion over CZO is enhanced by Ni, Cu, and Co
oxides. In the case of Ni–CZO, the oleic acid conversion
(89.7%) is much higher than the catalyst. On the contrary,
Mo oxide does not enhance the oleic acid conversion over
CZO. This is possibly due to the presence of non-sulfided
Mo content. Sulfided Mo catalysts are known to be active
and selective for C–O scission in DO reaction because the
presence of sulfur in the catalyst plays an important role in
the DO reaction.38 Therefore, non-sulfided Mo–CZO cat-
alyst is not suitable for DO reaction.
Table II summarizes the oxygen removal efficiency of
DO reaction products. The oxygen removal efficiency of
the Ni–CZO catalyst is 5 times higher than the blank test.
As a result, Ni–CZO catalyst exhibits the highest oxygen
removal efficiency among the prepared catalysts. Addition-
ally, the change in oxygen removal efficiency follows the
same trend as for oleic acid conversion.
CZO catalyst (824.43 ꢃmol
ity than Ni–CZO (692.15 ꢃmol
/g•catꢁ had the higher acid-
•NH3
/g•catꢁ. Wang et al.
•NH3
reported that higher acidity caused the production of light
compounds.19 It can be said that higher acidity was not
Delivered by Ingenta to: Nanyang Technological University
favorable due to the decrease of liquid yield and selectiv-
IP: 5.189.202.183 On: Thu, 09 Jun 2016 02:53:11
ity for C9∼C17 compounds. Therefore, Ni–CZO exhibits
Copyright: American Scientific Publishers
higher liquid yield (63.9%) than CZO (47.3%) due to the
lower acidity.
The above-mentioned reaction results can be explained
as follows the activity of Ni–CZO should be higher than
others because of the synergistic effects of Ni oxide and
the reducible CZO support. This is due to the reducible
oxide support (such as CeO2, TiO2, and ZrO2ꢁ and the fact
that free Ni plays an important role in the DO reaction,
which converts fatty acids to bio-diesel.21 Moreover, the
Figure 4 depicts selectivity for C9∼C17 compounds
(diesel fuel range) over Me–CZO catalysts. Interestingly,
Co–CZO catalyst exhibited very high oleic acid conversion
(84.7%), but selectivity for C9∼C17 compounds was 2.4%
lower than the blank test. Except for Co–CZO, all cata-
lysts exhibited higher C9∼C17 selectivity than the blank
test. The selectivity for C9∼C17 compounds decreased in
14
Catalyst : Ni-CZO
Reaction time = 3 h (Total = 27.3%)
12
Reaction time = 6 h (Total = 21.9%)
Reaction time = 12 h (Total = 17.3%)
30
27.3
10
+14.1%
8
6
4
2
0
20
18.1
16.4
15.9
+4.9%
+3.2%
+2.7%
13.2
–2.4%
10.8
10
9
10
11
12
13
14
15
16
17
0
Carbon number (#)
Blank
CZO
Ni-CZO Cu-CZO Co-CZO Mo-CZO
Figure 4. Selectivity of n-nonane (C9ꢁ to n-heptadecane (C17ꢁ over
Me–CZO catalysts (Me = Ni, Cu, Co, and Mo).
Figure 5. Distribution of linear hydrocarbons in the reaction product
with Ni–CZO as a function of reaction time.
4590
J. Nanosci. Nanotechnol. 16, 4587–4592, 2016

Shim et al.
Bio-Diesel Production from Deoxygenation Reaction Over Ce0ꢂ6Zr0ꢂ4O2 Supported Transition Metal
synergistic effects of nickel and Ce0ꢂ6Zr0ꢂ4O2, presence of
Catalyst : Ni-CZO
89.7
free Ni species, and the highest BET surface area. There-
fore, the Ni–CZO catalyst can be considered a promis-
100.0
100
80
60
40
20
0
95.7
ing DO catalyst for the bio-diesel upgrading process. An
optimum reaction time was found to be 3 h for Ni–CZO
catalyst to maximize diesel yield in the DO reaction.
Acknowledgments: This work was conducted under
the framework of Research and Development Program of
the Korea Institute of Energy Research (KIER) (B5-2451).
This work is financially supported by Korea Ministry of
Environment (MOE) as “Knowledge-based environmental
service (Waste to energy recycling) Human resource devel-
opment Project.”
3 h
6 h
12 h
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oleic acid conversion (89.7%), selectivity for C9∼C17 com-
pounds (27.3%), and oxygen removal efficiency (48.3%)
ꢀ
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J. Nanosci. Nanotechnol. 16, 4587–4592, 2016
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Received: 12 September 2014. Accepted: 18 November 2014.
Delivered by Ingenta to: Nanyang Technological University
IP: 5.189.202.183 On: Thu, 09 Jun 2016 02:53:11
Copyright: American Scientific Publishers
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