Sci. Bull. (2015) 60(24):2096–2106
com
DOI 10.1007/s11434-015-0971-0
Review
Recent advances for the production of hydrocarbon biofuel
via deoxygenation progress
Dan Li • Hui Xin • Xiangzhe Du • Xiaolei Hao •
Qingxue Liu • Changwei Hu
Received: 17 November 2015 / Accepted: 4 December 2015 / Published online: 22 December 2015
Ó Science China Press and Springer-Verlag Berlin Heidelberg 2015
Abstract The current world energy crisis and increasing
environmental concerns over global climate change from
combusting fossil fuel are driving researchers into a new
route to produce fuels via sustainable resource to meet the
demands of human. In recent years, deoxygenation as an
alternative method has been applied in the production of
hydrocarbon fuels, particularly via the deoxygenation of
fatty acids and triglycerides from seed oils and fats, pro-
ducing hydrocarbon fuels entirely fungible with fossil
fuels. The deoxygenation of biobased feedstock to fuel-like
hydrocarbons is critically reviewed in this article. The
review mainly discusses the use of feedstock, innovation of
catalysts, and the reaction mechanism involved in the
production of hydrocarbon fuels via deoxygenation
progress.
Keywords Deoxygenation
Biobased feedstock

Hydrocarbon fuels
Deoxygenation mechanism
1 Introduction
The decline of fossil resources and environment crisis are
driving our society to search for new sources for the pro-
duction of fuels. Thus, the research and development on
biomass-derived feedstocks are intensively reported all
D. Li
X. Du
X. Hao
Q. Liu
C. Hu (&)
Key Laboratory of Green Chemistry and Technology, Ministry
of Education, College of Chemistry, Sichuan University,
Chengdu 610064, China
e-mail: changweihu@scu.edu.cn
H. Xin
College of Chemical Engineering, Sichuan University,
Chengdu 610065, China
123
www.scibull.
www.springer.com/scp
Materials Science
over the world. During the past years, many biofuel pro-
duction technologies have been developed depending on
the biobased feedstock available. For instance, the thermal
and catalytic cracking (pyrolysis) of biomass can obtain
bio-oil from raw biomass feedstock [1–3]. However, the
products are complex, and even a number of undesirable
compounds are obtained. Therefore, the above products
need to be upgraded before being used as fuel.
The most promising way to get fuel fungible with fossil
fuels is to use natural vegetable oils and animal fats to
produce fuel. There are generally two technical routes for
this purpose: (1) Transesterification/esterification reaction
can be applied in converting renewable feeds (veg-
etable oils and animal fats) into fatty acid methyl esters
(FAMEs) used as biodiesel [4, 5]. However, FAMEs do not
change the relative oxygen content and still has high
oxygen content compared to petroleum-derived fuels,
which lead to the relatively poor calorific value, the low
stability and high viscosity [6]; (2) the removal of oxygen
from vegetable oils and animal fats is the most promising
technology to obtain high-grade fuel, which provides a
drop-in replacement for fossil fuel [7–9]. As the compo-
sition and chemical structure of high-grade fuel, obtained
from the deoxygenation of vegetable oils and animal fats,
is similar to fossil fuel, it can be directly used by the engine
of traditional machines without remolding the existing
fuel-burning equipment. Currently, three approaches have
been adapted to remove oxygen from fatty acids and fatty
acid ester, as shown in Scheme 1 [9] and Scheme 2,
respectively. The degree of consumption of H2 follows
the order: decarboxylation (deCO2) \ decarbonylation
(deCO) \ hydrodeoxygenation (HDO) in Scheme 1.
This article reviews the present status of the deoxy-
genation conversion of fatty acids and fatty acid ester into
biofuels. This contribution focuses mainly on the
Sci. Bull. (2015) 60(24):2096–2106
Scheme 1 Three pathways proposed for the deoxygenation of a fatty
acid into hydrocarbons. I deCO2, II deCO, III HDO
feedstocks, catalyst types, and the conversion mechanism
of model compound and biomass feedstock into hydro-
carbon fuels via deoxygenation progress.
2 Feedstock
Nowadays, fatty acid, fatty acid ester, and vegetable oil
have been used as resource for the production of biofuels
owing to their renewability and low cost [7–28].
2.1 Fatty acid and fatty acid ester
As the structures of fatty acid and fatty acid ester are
similar to vegetable oils, most deoxygenation studies are
performed on model compounds. Stearic acid (SA) is the
Scheme 2 Pathways proposed for the deoxygenation of a fatty acid ester into hydrocarbons and different definitions of deoxygenation reaction
2097
most widely investigated model compounds for the
deoxygenation reaction of feedstock. For instance, Bezer-
gianni et al. [26] found that n-heptadecane was as major
deoxygenation product over Ni/Al2O3, Pt/Al2O3, and Pd/
Al2O3 catalysts, whereas the high n-heptadecene selectivity
over Cu/Al2O3 might be explained by the poor hydro-
genation properties of Cu. Murzin and co-workers [27, 28]
reported that the C-supported Pd catalyst facilitated better
decarboxylation of SA compared to C-supported Pt, Ni,
Rh, Ir, Ru, and Os. Immer et al. [6] documented further that
the 5 wt% Pd/C catalyst under He assisted the deoxy-
genation of SA primarily via decarboxylation, whereas that
of oleic acid (OA) via decarbonylation. For unsaturated
C18 free fatty acids, they found that the unsaturated C18
free fatty acids must be hydrogenated to SA before
decarboxylation could proceed at a significant rate. OA
deoxygenation occurred very slowly under He primarily
via decarbonylation. In contrast, OA deoxygenation
occurred under 10 % H2 facilely via hydrogenation to SA
followed by decarboxylation.
As palmitic acid is the main composition of palm oil, it
has been studied to obtain high-grade fuel via deoxy-
genation method. Peng et al. [7] studied the deoxygenation
of palmitic acid over a variety of sulfur-free supported
metal catalysts in the presence and absence of H2. They
found that Pd favored CO2 formation by direct decar-
boxylation, whereas Pt and Ni preferentially catalyzed the
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decarbonylation in the absence of H2. Liu et al. [9] used
NixPy/HZSM-22 catalysts to convert palmitic acid to die-
sel-like hydrocarbons under ambient pressure in the
absence of any solvents. And NixP facilitated the decar-
bonylation and decarboxylation.
Han et al. [29] transformed higher aliphatic esters into
diesel-like paraffins by an efficient decarboxylation
method. The decarboxylation of aliphatic esters could be
successfully performed with high selectivity over a Pd/
BaSO4 catalyst in supercritical hexane at a much lower
temperature. Hari and Yaakob [25] used non-sulfided
CoFe/c-Al2O3 catalyst to hydrotreat FAMEs derived from
jatropha oil. Effect of reaction temperature and time was
investigated on the FAME conversion and diesel selectiv-
ity. The major products obtained were straight chain
alkanes in the range C15–C18. Fe incorporation facilitated
the cobalt oxide reduction by H2 spill over and cobalt oxide
dispersion which facilitate C–O bond activation and
breaking.
Both saturated and unsaturated feeds can be deoxy-
genated via deCO/deCO2. The reaction pathways obtained
are particularly sensitive to the reaction conditions, such as
feeds, reaction gas, and catalysts. Furthermore, the reaction
pathway of unsaturated feeds was firstly hydrogenated to
saturated and then followed to be deoxygenated. Pd-based
catalyst favored CO2 formation by direct decarboxylation,
whereas Pt and Ni preferentially catalyzed the decarbony-
lation in the absence of H2.
2.2 Vegetable oils
Catalytic deoxygenation of vegetable oils is an important
reaction for the production of biodiesel. Numerous types of
vegetable oils have been identified for potential use as raw
materials of fuel production. The vegetable oil is divided
into edible and non-edible oil. Table 1 shows fatty acid
compositions found in the different vegetable oils [30].
2.2.1 Edible oil
Many types of edible vegetable oils, including soybean oil
(SBO), sunflower oil (SFO), rapeseed oil (RSO), and corn oil
(CO), have been investigated as renewable biomass-derived
feedstocks in the production of biofuels [31–39]. It can be
seen that SBO and SFO mainly contain the linoleic, oleic,
and palmitic acid in Table 1. Wang et al. [40] devised a new
method to produce low cloud point, high-quality diesel by
combining the deoxygenation and isomerization of SBO.
The SBO was converted to i-C15, i-C16, i-C17, and i-C18
alkanes via decarboxylation, decarbonylation, hydrodeoxy-
genation, and isomerization pathways over the bifunctional
catalysts. Lou and co-workers [41] investigated the
hydrodeoxygenation of SFO over 5.0 wt% Pd/Al-SBA-15
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and Pd/HZSM-5(22) in an autoclave. They discovered that
the strong acidity of the catalysts was not favorable for
converting SFO into C15–C18 diesel-like hydrocarbons at a
high temperature of 300 °C. Meanwhile, Lou and co-work-
ers [42] reported one-step hydrodeoxygenation and isomer-
ization of SFO on different loading Mo2C/CNTs catalysts.
The mass ratio of SFO with catalyst could affect feedstock
conversions and product yields. With the mass ratio of SFO
with Mo2C reduced, the hydrocarbon yields and percentage
of branched alkanes increased and reached a maximum
hydrocarbon yield of 87 % with 55 % branched alkanes at
the mass ratio of 7.5.
Linoleic and oleic are the main compositions of RSO
and CO, respectively (Table 1). Kubicka and Kaluza [31]
investigated the effect of active metals on deoxygenation
pathway in hydrotreatment of RSO over sulfided Ni/Al2O3,
Mo/Al2O3, and NiMo/Al2O3 catalysts. Botas et al. [36]
investigated that the RSO conversion using Mo oxide- and
Ni-modified nanocrystalline ZSM-5 zeolites as catalysts in
a nitrogen atmosphere. The incorporation of metals into the
ZSM-5 support influenced their acid, textural properties,
and catalytic behavior. Recently, Botas et al. [35] had a
new discovery about Ni-modified nanocrystalline and
hierarchical ZSM-5 on the conversion of RSO into fuels.
The main products were gaseous olefins (mostly ethylene
and propylene) and aromatic compounds (benzene,
toluene, and xylenes). Furthermore, high hydrogen con-
tents were found in the gaseous stream, which were
attributed to the operating conditions employed (high
reaction temperature and atmospheric pressure).
The deoxygenation products have been observed to
highly dependent on catalyst types and feed-to-catalyst
ratio. The different mass ratio of feeds with catalysts could
affect feedstock conversions and products yields. It is
important to note that high costs are associated with bio-
diesel production from edible oils because of their high
market price.
2.2.2 Non-edible oil
The use of non-edible oil over edible vegetable oils is
always preferred for the food versus fuel dilemma. Several
studies have been dedicated to investigate the deoxygena-
tion of non-edible vegetable oils. The conversion of non-
edible jatropha oil to biofuels is a promising route for many
reasons: high energy density, easy conversion to liquid
biofuel, high oil production at a low price, ease of estab-
lishing and maintaining jatropha plantation, government
support, etc. [43]. Gong et al. [38] investigated the
hydrotreatment of jatropha oils over PtPd/Al2O3 and
NiMoP/Al2O3 catalysts in a fixed-bed reactor. Removing
the oxygen from jatropha oil over PtPd/Al2O3 catalyst was
primarily completed through decarboxylation and/or
Sci. Bull. (2015) 60(24):2096–2106 2099

Table 1 Fatty acid composition of different vegetable oils

Fatty acid composition (wt%)
Palmitic (16:0, Stearic (18:0, Arachidic (20:0, Oleic (18:1, Linoleic (18:2, Linoleic (18:3, Ricinoleic
C16H32O2) C18H36O2) C20H40O2) C18H34O2) C18H32O2) C18H30O2) (C18H30O2)

Edible oil
SBO 12 3 0 23 55 0 0
SFO 6 3 0 17 7 6 0
RSO 3 1 0 4 22 8 0
CO 12 2 Tr-trace 25 6 Tr 0
Non-edible oil
Jatropha oil 16 6 0 43 34 0.8 0
Rubber seed oil 10 8 0 24 39 16 0
Castor oil 1 1 0 3 5 0 88
Karanja oil 11 7 0 51 16 2 0
Polanga oil 12 13 0 34 38 0.3 0

decarbonylation. Meanwhile, a series of sulfided NiMo/
SiO2-Al2O3 and NiMo/ZSM-5-Al2O3 catalysts are pre-
pared and used in hydrotreatment of jatropha oil in a fixed-
bed flow reactor [44]. Liu et al. [39] synthesized bioavia-
tion fuel by hydroprocessing castor oil using bifunctional
catalysts with differing acid strength. Highest aviation
range alkane yields (91.6 wt%) were achieved with high
isomer/n-alkane ratio (4.4–7.2) over Ni supported on acidic
zeolites. Meanwhile, the HDO product prepared was
compared with jet fuel No. 3, which showed that the HDO
product met the basic jet fuel mixing requirements.
The use of waste cooking oil (WCO) has triggered
increasing interest in catalytic deoxygenation for the pro-
duction of biofuels due to their costs at least 2–3 times
cheaper than virgin vegetable oils. Bezergianni and co-
workers [45–50] investigated catalytic conversion of WCO
with sulfided and acid catalysts to produce diesel. Firstly,
Bezergianni et al. [47] focused on the use of WCO as the
main feedstock for producing biodiesel on the same com-
mercial hydrotreating catalyst, but three parameters were
considered for evaluating the effectiveness of this technol-
ogy, pressure, hydrogen-to-oil ratio, and liquid hourly space
velocity (LHSV). In this way, they studied the effect of
temperature on product yields, heteroatom removal, and
hydrocarbon composition for the WCO conversion of bio-
diesel production. After hydrotreatment, the H/C ratio was
increased from 0.15 to 0.17, whereas the liquid density of the
oil decreased from 0.858 to 0.757 g/cm3 for the final product
[48, 49]. However, a major disadvantage for this liquid fuel
was the poor flow properties at cold temperatures.
Microalgae are attractive biomass feedstock to produce
biofuels owing to high cellular lipid contents and high
photosynthetic rates. Microalgae grow 12 times faster and
yield 30 times more triglycerides compared to conventional
rape oil. Furthermore, microalgae do not need arable land
and only need waste water to provide a nitrogen source and
industrial CO2 to boost algae biomass. Therefore,
microalgae become a promising green energy bioresource.
Currently, the deoxygenation approach is used for
microalgae oil refining. Lercher and co-workers [7] used Ni
supported on zeolite HBeta to quantitatively convert the
crude microalgae oil under mild conditions (260 °C, 40 bar
H2, 1 bar = 105 Pa) to diesel-range alkanes as high-grade
second-generation transportation biofuels. Lercher and co-
workers [51] extended their researches on the deoxygena-
tion pathway of microalgae oil by investigating the reaction
mechanism over Ni/ZrO2 catalyst in details.
Although the conversion of non-edible oils into biofuel
has been widely studied, the conversion mechanism is still
obscure. Furthermore, the conversion technique of non-
edible oil cannot be applied in industry.
3 Catalysts
Most processes for the catalytic deoxygenation of veg-
etable oil and animal fat are hydroprocesses and thus
require H2. The catalysts used in these processes are gen-
erally divided into two categories: noble metal catalyst and
non-noble metal catalysts. Additionally, transition metal
phosphides have triggered increasing interest in catalytic
deoxygenation due to their excellent catalytic performance
[52–56].
3.1 Noble metal catalysts
Noble metal catalysts have been applied along the years for
hydrogenation of vegetable oils and fatty acids in Table 2.

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Table 2 Conversion of feedstock into biofuels on noble metal catalyst
Catalyst Conversion (%)
Pd/C 100
Pd/C 74–100
Pd/C 98
Pd/C 32–100
5 % Pt/C 85–95
5 % Pt/C 39–99
Murzin and co-workers [10, 20, 28] have studied exten-
sively on liquid-phase deoxygenation of fatty acid esters
(FAs) for biofuel production. With regard to metal loading,
when 1 wt% and 4 wt% Pd/C catalysts with almost iden-
tical metal dispersions were tested in tall oil fatty acid
(TOFA) deoxygenation, the higher loaded catalyst gave
better results, which suggests that higher metal loadings
(and hence increased numbers of active sites) are beneficial
for fatty acid deoxygenation.
Fu et al. [57] reported the conversion of saturated and
unsaturated fatty acids to alkanes over Pt/C in high-tem-
perature water. The advantage of the reactions was that
they could be performed with no addition of H2. The sat-
urated fatty acids exhibited high selectivity to the decar-
boxylation products (n-alkanes), while the unsaturated fatty
acids gave the corresponding decarboxylation products
with low selectivity. Na et al. [58] investigated the
deoxygenation of microalgal oil for the production of
hydrocarbon fuel on Pt-based supported catalyst. Activated
carbon support showed better performance than silica as a
support. The 5 wt% platinum supported on activated car-
bon (5 wt% Pt/C) was an optimized catalyst.
Recently, the noble bimetallic catalysts were prepared
using an ion exchange procedure by Lamb and co-workers
[59]. They studied the catalytic deoxygenation of octanoic
acid ton-heptane over silica-supported Pd and PdAu cata-
lysts in a fixed-bed microreactor. Catalyst stability without
significantly affecting decarbonylation activity was
improved over alloying Pd with Au catalysts.
In view of the above results, the conversion of fatty
acids and their derivatives to hydrocarbons via deCO/
deCO2 has been mostly studied over Pd and Pt catalysts,
and carbon materials have been found to be favored cata-
lyst support. However, carbon materials might also bring
some troublesome issues considering the catalyst
reusability. Furthermore, the high cost of these precious
metals represents an important drawback from an eco-
nomic standpoint, which prevents their wide application.
Additionally, the noble bimetallic catalysts do not improve
significantly the catalytic performance.
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Sci. Bull. (2015) 60(24):2096–2106
Conditions
T (°C), P (MPa), WHSV (h-1) References
T = 300, P = 0.6, batch [42]
T = 300–360, P = 1.5–2.7, batch [20]
T = 300, semibatch [28]
T = 300–360, P = 1.7–4.0, batch [10]
T = 330, batch [57]
T = 360, P = 10, autoc [58]
3.2 Non-noble metal catalysts
3.2.1 Sulfided catalysts
Ni-/Co-/Mo-based catalysts are widely applied in various
systems due to lower costs and high activity [60–64].
The hydrotreating sulfide catalysts have been applied for
producing hydrocarbons from fatty acids, triglycerides,
and vegetable oils in Table 3. Ruiz et al. [65] investi-
gated the hydrodeoxygenation of 2-methoxyphenol
(guaiacol) over MoS2 catalysts supported on different
activated carbons, which were different in porosity and
oxygen surface functionality. The activity differences on
the different carbon supports were correlated with the
dispersion of MoS2. Lower catalyst dispersion and lower
HDO activity might be attributed to greater abundance of
surface oxygen groups (mainly carboxylic, quinonic, and
lactonic groups) on the support. However, the
monometallic sulfide catalysts are less active than the
bimetallic ones, which is in agreement with the activity
trends reported for hydrodesulfurization. Sulfide NiMo
bimetallic sulfide catalyst yields both hydrodeoxygena-
tion and hydrodecarboxylation products in the conversion
of RSO, whereas NiS yields exclusively hydrodecar-
boxylation products and Mo sulfide catalyst almost
exclusively hydrodeoxygenation products [36]. Then,
deoxygenation of triglycerides over Co/Mo sulfides sup-
ported on different mesoporous molecular sieves (MCM-
41) (varying Si/Al ratio) was investigated by Kubicka
et al. [66]. Incorporation of Al into the framework of
MCM-41 led to an increase in both conversion of
triglycerides and selectivity to n-heptadecane and n-oc-
tadecane, respectively. However, the conversion of
triglycerides was lower than that achieved over alumina-
supported CoMo.
Although sulfide catalysts can replace the noble catalyst
to convert biomass feeds into hydrocarbon fuel, they can-
not be reused by simple regeneration method due to sulfur
losing from catalyst active sites, which would affect
adversely the deoxygenation of triglycerides [67].
Sci. Bull. (2015) 60(24):2096–2106
Table 3 Sulfided transition catalysts, feedstock, operating conditions used for the study of catalytic deoxygenation of model compound
Catalyst Feedstock
Sulfided NiMo/SiO2-Al2O3 Vegetable oil
MoS2 on activated carbon Guaiacol
Sulfided CoMo/MCM-41 Triglycerides
Sulfided CoMo/Al2O3 RSO
Oxidic and sulfided NiMo/Al2O3 RSO
Sulfided NiMo/Al2O3 and CoMo/Al2O3 WCO
3.2.2 Non-sulfide catalysts
Non-sulfide catalysts have been used for the vegetable oil
and fatty acids deoxygenation reactions in Table 4. RSO
hydrotreating experiments involving NiMo on alumina
were found to provide substantially higher hydrocarbon
compared to those conducted with monometallic catalysts,
such as Ni or Mo, on alumina. Meanwhile, the selectivity
to hydrocarbons can be enhanced using a bimetallic cata-
lyst. In addition, it was reported that the atomic ratio of Ni/
Mo in bimetallic catalysts did not significantly change the
product distribution [31].
Kubicka and co-workers [34] used a commercial
hydrotreating Ni–Mo/alumina catalyst to convert RSO into
biodiesel. Reaction products mostly contained n-heptade-
cane and n-octadecane accompanied by low concentrations
of other n-alkanes and i-alkanes. However, the products
had worse low-temperature properties, even after addition
of high concentrations of flow improvers. They further
investigated different precursors with different Ni species
distribution in order to understand the effect of catalyst
preparation on the activity/selectivity of NiMo-alumina
catalysts in the deoxygenation of RSO. Veriansyah et al.
[68] studied the effects of various supported catalysts on
the hydroprocessing of SBO. The order of the hydropro-
cessing conversion was NiMo (92.9 %) [ Pd (91.9 %) [
CoMo (78.9 %) [ Ni (60.8 %) [ Pt (50.8 %) [ Ru
(39.7 %) at the catalyst/oil weight ratio of 0.044, and Ni
(95.9 %) [ NiMo (91.9 %) [ Pd (90.9 %) [ CoMo
(79.9 %) at 0.088. When Ni or Pd catalysts were used,
straight chain n-C17 and n-C15 alkanes were the most
abundant composition in the liquid, whereas enhanced
isomerization and cracking reaction activity might produce
lighter and isomerized hydrocarbons on the CoMo catalyst.
Combined with gas-phase and liquid product results,
decarboxylation was a dominant reaction pathway when
the Pd catalyst was used, while hydrodeoxygenation was
favored when the NiMo or CoMo catalyst was used [68].
2101
Conditions
T (°C), P (MPa), WHSV (h-1) References
T = 350; P = 4; LHSV = 7.6–1 [63]
T = 300, P = 5, batch [65]
T = 300, 320, P = 2–12, cont [66]
T = 310, P = 3, cont [67]
T = 350–400, P = 1–20, cont [42]
T = 330–390, P = 1–20, cont [46]
Molecular sieve materials are the most suitable catalysts
for the conversion of triglyceride-based oil into biofuel due
to their highly ordered structures and uniform pore size,
which can provide high activity, remarkable selectivity, and
strong resistance to deactivation. In this way, different
researches have been reported on zeolites catalysts for the
production of hydrocarbons from RSO. Botas et al. [36]
investigated the RSO conversion using Mo oxide- and Ni-
modified nanocrystalline ZSM-5 zeolites as catalysts in a
nitrogen atmosphere. The incorporation of metals into the
HZSM-5 support influenced their acidic and textural prop-
erties, and catalytic behavior. Ni/HZSM-5 catalyst exhib-
ited remarkable selectivity toward the formation of light
olefins, whereas Mo/HZSM-5 catalyst was favorable for the
formation of aromatics. Meanwhile, a great amount of
highly polyaromatic coke was observed over the Ni/HZSM-
5 samples, while a less structured coke was deposited on the
Mo/HZSM-5 catalysts. Recently, Botas et al. [35] studied
the Ni-modified nanocrystalline and hierarchical ZSM-5 on
the conversion of RSO into fuels. The main products were
gaseous olefins (mostly ethylene and propylene) and aro-
matic compounds (benzene, toluene, and xylenes). And the
high hydrogen contents were found in the gaseous stream,
which were attributed to the operating conditions employed
(high reaction temperature and atmospheric pressure). The
coke observed over Ni-containing ZSM-5 samples was in
the form of carbon nanotubes, which induced a segregation
of the Ni particle from the zeolite support. This effect was
attenuated in the hierarchical zeolites because the secondary
porosity stabilized the metal particles.
Based on the fact that long-chain alkanes are the major
products of these catalytic deoxygenation processes over
Ni/Mo supported on Al2O3, these products exhibit poor
performance at low temperatures because of their high pour
and cloud points. The high-quality fuel can be attained on
the molecular sieve materials catalyst. Ni/Mo bimetallic
catalysts provide substantially higher hydrocarbon yields
compared to those conducted with monometallic catalysts.
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Table 4 Non-sulfide Ni-/Mo-based catalysts used for the vegetable oil and fatty acids deoxygenation reactions
Catalyst Feedstock Conditions
T (°C), P (MPa), WHSV (h-1) References

Ni/USY-MCM, Ni/USY-APTES-MCM-41 Castor oil T = 300, P = 3, WHSV = 2 [52]

20 % Ni/C Tristearin T = 350, P = 6.8, batch [14]
NiMo/c-Al2O3 Pyrolysis oil T = 100, P = 3, batch [68]
NiMo/Al2O3 RSO T = 260–280, P = 3.5, WHSV = 1–4, H2/oil = 50 mol/mol [33]
NiMo/Al2O3 RSO T = 310–360, P = 7–15, WHSV = 1.0, H2/oil = 920 N m3/m3 [34]
NiMo/Al2O3, Mo/Al2O3, Ni/Al2O3 RSO T = 260–280, P = 3.5, WHSV = 0.25–4.0 [31]

3.2.3 Transition metal phosphides
Transition metal phosphides show similar chemical prop-
erties to noble metals. Early, transition metal phosphides
have been applied in the hydrodesulfurization [69–72]. To
date, some researchers found that Ni2P-based catalysts
exhibited excellent catalytic deoxygenation performance
(Table 5). Yang et al. [19] comparatively investigated the
catalytic performances of Ni2P/SBA-15 and Ni/SBA-15
toward the deoxygenation of methyl oleate. Ni2P/SBA-15
exhibited higher catalytic decarboxylation activity than Ni/
SBA-15. Chen et al. [16] demonstrated that Ni2P/SiO2
provided higher total selectivity to n-C11 and n-C12 in the
deoxygenation of methyl laurate than Ni/SiO2, whereas Ni
produced more cracked products.
It was determined that transition metal phosphides
exhibited particular deoxygenation activity. Liu et al. [9]
investigated the effect of the nickel-to-phosphorus molar
ratio on the formation and dispersion of different nickel
phosphide species and on the deoxygenation performance
using palmitic acid as a model compound in details.
Recently, Moon et al. [73] investigated the hydrodeoxy-
genation reaction on Ni2P-based catalysts. The Ni2P/SiO2
gave an HDO conversion over 90 % with two different
reaction pathways: (1) At 1 atm (1 atm = 1.01325 9
105 Pa), the direct deoxygenation was dominant to produce
benzene; and (2) at 8 atm, prehydrogenation followed by
deoxygenation was preferred to produce cyclohexane.
Combining the X-ray absorption fine structure spec-
troscopy results with density functional theory (DFT)
analysis, they concluded that the active site of Ni2P cata-
lysts was composed of threefold hollow Ni and P sites
which led to adsorption of H or OH groups. The HDO
conversion of guaiacol over Ni2P/SiO2, Ni2P/ZrO2, and
Ni2P/AC catalysts was studied. The activity results sug-
gested that the catalyst performances of Ni2P/ZrO2 and
Ni2P/AC were superior to the Ni2P/SiO2 catalyst.
Transition metal phosphides exhibit particular deoxy-
genation activity. Ni2P-based catalysts exhibit higher cat-
alytic decarboxylation activity than Ni-based and can
entirely replace the noble catalysts applied in the deoxy-
genation of vegetable oil and animal fat. Thus, Ni2P-based
catalyst has been suggested to be a promising catalyst for
the production of green diesel.
4 The reaction mechanism
In the study of triglyceride and related feedstock deoxy-
genation over supported metal catalysts, different reaction
mechanisms have been proposed based on the activity
results and in situ technology.

Table 5 Transition phosphide catalysts, feedstock, operating conditions used for the study of catalytic deoxygenation of different model
compound
Catalyst Feedstock Conditions
T (°C), P (MPa), WHSV (h-1) References

Ni2P/SiO2 Guaiacol T = 280–380, P = 0.1, 0.8, WHSV = 2, cont [6]

Ni2P/SBA-15 Methyl oleate T = 250–340, P = 0.3–4.0, WHSV = 20, cont [16]
Ni2P/SiO2 Guaiacol T = 250–300, P = 0.1–0.8, LHSV = 2.0, cont [73]
Ni2P/SiO2, CeO2, TiO2, SAPO-11 Methyl laurate T = 300–314, P = 3, WHSV = 10, cont [19]
Ni2P/SiO2 Algae T = 500, P = 0.1 [20]
NixP/HZSM-22, Ni2P/HZSM-22 Palmitic acid T = 310–360, P = 0.1 [9]

123
Sci. Bull. (2015) 60(24):2096–2106
4.1 The reaction mechanism of fatty acid conversion
into biofuel
Recently, in situ IR spectroscopy has been used to monitor
the variation of the concentrations of reactants and inter-
mediates during the reactions, as well as that of the
adsorbed species on the surface of the catalysts (ZrO2 and
Ni/ZrO2) in the presence and absence of H2. Peng et al. [7]
proposed the reaction mechanism for the conversion of
palmitic acid on ZrO2-supported metal catalysts. On ZrO2,
ketonization was the dominant reaction. ZrO2-supported
metal catalysts involved initial adsorption of the substrate
at oxygen vacancies of ZrO2 to form palmitate, which was
then transformed to the adsorbed ketene through H
abstraction and H2O elimination.
The adsorbed ketene follows different reaction routes
dictated by the reactive gas environment. In H2, the ketene
is hydrogenated to hexadecanal at the metal site. In the
absence of H2, the ketene combines with a neighboring
palmitate molecule on the ZrO2 surface to form palmitone.
Scheme 3 Four catalytic pathways proposed for the deoxygenation of palmitic acid on 40NiPZ. a Decarbonylation, b decarboxylation, c initial
isomerization, d initial isomerization and cracking
2103
Liu et al. [9] reported a new decarbonylation and decar-
boxylation mechanism of palmitic acid based on in situ
DRIFT spectroscopy. The plausible deoxygenation path-
ways over 40NiPZ are shown in Scheme 3. The key step
was H2 dissociation on NixP (Ni12P5 and Ni2P) and then
combination of H with OH (in palmitic acid) to form H2O,
generating the C14H29-CH2-CHO intermediate observed by
in situ DRIFT. Simultaneously, palmitic acid could be
converted into aromatic hydrocarbons (or short chain
hydrocarbons) and CcHd–COOH via cracking and isomer-
ization. Finally, CcHd–COOH could be further converted
into hydrocarbons by decarbonylation and decarboxylation.
In fact, Crocker and co-workers [14] also observed that
the use of supported metal catalysts typically afforded
hydrocarbons containing less number of carbon atoms than
the feed via decarboxylation and/or decarbonylation path-
ways, although symmetrical ketones were sometimes
observed in small amounts as unwanted side products.
Meanwhile, Berenblyumet al. [74] chose the conversion of
propionic acid over a Pd catalyst as a model system and
123
2104
investigated the decarboxylation and decarbonylation
pathways by DFT calculations. They inferred that the rate-
determining step might be C–C bond cleavage in the
coordinated carboxylic acid moiety. Decarboxylation is
thermodynamically preferred, suggesting that the decar-
bonylation reaction is preferred for kinetic reasons. It is
worth noting that hydrogenation of the olefin produced
during decarbonylation provides an energy gain which
renders the pathway thermodynamically more favorable.
However, the majority of the hydrodeoxygenation reac-
tions stem from side reactions accompanying deCO/
deCO2, which might induce the occurrence of reverse
water–gas shift (RWGS) and methanation reactions must
be watched closely [8].
4.2 The reaction mechanism of fatty acid ester
conversion into biofuel
Lou and co-workers [29] studied the transform of aliphatic
esters into high-energy alkanes over palladium-supported
on barium sulfate catalyst and proposed the decarboxyla-
tion mechanism according to the comprehensive analysis
of gas and liquid products (Scheme 4). The results showed
that aliphatic esters underwent cleavage of the alkyl-oxy-
gen bond and the acyl-oxygen bond, respectively. Aliphatic
esters were converted into CnH2n?2 through decarboxyla-
tion route (cycle 1) accompanied by decarbonylation
reaction (cycle 3). Since neither nonadecane nor nonane
could be detected in the corresponding liquid products,
CnH2n?1CH3 might derive from aliphatic acid parts of
carboxylic esters by complete hydrodeoxygenation (cycle
2) rather than by coupling of R1 radical with R2 radical.
Then, Bezergianni et al. [48] continued to study the one-
step hydrodeoxygenation and isomerization mechanism of
esters over Mo2C/CNTs catalyst. They speculated that the
acyl C–O bond cleavage of esters occurred initially with
acyl complexes generated on Mo2C surface, and the acyl
complexes experienced one of the possible reaction routes.
Scheme 4 Plausibel decarboxylation mechanism of aliphatic esters
123
Sci. Bull. (2015) 60(24):2096–2106
From the above results, we can deduce the different tran-
sition mechanisms of esters over different catalysts.
4.3 The reaction mechanism of vegetable oil
conversion into biofuel
As reported by Wang et al. [40], the strong Lewis acids
played an important role in causing hydrodeoxygenation
reactions. Thus, plausible pathways were speculated
according to the results obtained over different metal/sup-
port catalysts. The deoxygenation of vegetable oil
(triglyceride) underwent two parallel pathways: (1)
involving the decarboxylation and decarbonylation occur-
red on the metal site dispersed on the zeolite support or the
c-Al2O3; and (2) involving the hydrodeoxygenation, which
proceeded on the metal and strong Lewis acidic sites dis-
persed on the outer surface of the small zeolite crystals or
the amorphous phase of the c-Al2O3 to generate n-alkane
with the same carbon number as the fatty acid chain in the
triglyceride. The n-alkanes generated from these two
pathways would be isomerized on the metal sites and the
Brønsted acid sites in the next step.
5 Conclusions
The conversion of renewable feedstock to fuel-like
hydrocarbons via deoxygenation represents a promising
alternative to produce biofuel, which can be used as those
from fossil feedstock. Nevertheless, several challenges
need to be overcome before realizing this goal.
Researchers have focused mainly on the deoxygenation
of model compounds; however, the compositions of raw
biomass oil are complex and often contain different fatty
acid and esters. Thus, new catalysts and new catalytic
process should be researched more specifically for different
raw biomass feedstock.
The complex composition of raw biomass feedstocks
can hinder the selectivity and activity of catalysts in the
conversion into biofuels. Additionally, the deactivation of
the catalysts represents one of the greatest difficulties in
deoxygenation. Regardless of noble and non-noble metal
catalyst, even minimal coke formation would make the
catalyst poisoned and induce deactivation. Therefore, new
kinds of catalysts, which can be resistant to coke formation
or be regenerated by simple processes, must be developed
in the future.
The deoxygenation mechanism of the model compound is
relatively clear over model catalysts, whereas the deoxy-
genation mechanism of raw feedstock has been reported
rarely. The use of raw biomass feedstock to produce biofuels
preserves perspective future research. Therefore, the
Sci. Bull. (2015) 60(24):2096–2106
deoxygenation mechanism of biomassed feedstock should
be focused especially for the conversion of raw biomass
feedstock with the help of advanced in situ technology.
Finally, as mentioned above, economic considerations also
favor the development of catalysts based on non-noble metals.
Acknowledgments This work was supported by the National Nat-
ural Science Foundation of China (21303109) and the Application
Foundation Program of Sichuan Province (2013JY0007).
Conflict of interest The authors declare that they have no conflict
of interest.
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