Renewable and Sustainable Energy Reviews 48 (2015) 240–255

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Green diesel synthesis by hydrodeoxygenation of bio-based

feedstocks: Strategies for catalyst design and development
n
Naveenji Arun, Rajesh V. Sharma, Ajay K. Dalai
Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon, SK, Canada S7N
5A9

article info abstract

Article history: Green diesel or straight chain hydrocarbons are produced by the hydrodeoxygenation of bio-based feedstocks such as
Received 12 July 2013 vegetable oils and bio-oils. Usage of green diesel for commercial purpose can be economical to cater the energy demands of
Received in revised form the present generation. Traditionally, transition metal sulfides have been used for hydrotreating reactions and more recently
25 August 2014 usage of transition metallic carbide, nitride, boride and phosphide catalysts are gaining importance. In this comprehensive
Accepted 7 March 2015 review, it is intended to focus on some major developments in catalyst design methodology pertaining to hydrodeoxygenation
(HDO) reaction systems. The details related to the different catalysts used for the hydrodeoxygenation reaction are also
Keywords: discussed. Most of the research works have been carried out using model compounds such as guaiacol and phenol using
Green diesel moderately-highly acidic supports such as Al2O3, ZrO2 and TiO2 and active metals such as palladium, platinum, nickel and
Hydrodeoxygenation
molybdenum. Factors to be considered for the choice of feed stock, selection of support material, active metals, promoters and
Bio-based feedstocks
their influence on the hydrodeoxygenation reaction, catalyst design procedure, catalyst preparation method and the influence
Catalyst design
of the catalyst treatment methods on the morphology of catalyst and their performance are discussed in this review paper.
Most research works have focused on usage of acidic support materials and focus on basic support materials is scarce. Choice
is promoters is highly dependent on the promoter–support interaction and it is essential to ensure minimum promoter– support
interaction for the efficient performance of the catalyst.

& 2015 Published by Elsevier Ltd.

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

2. Hydrodeoxygenation (HDO) process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241

2.1. Reaction scheme for direct hydrodeoxygenation (Eq. (1)) and decarboxylation (Eq. (2)) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3. Feed source for hydrodeoxygenation reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4. Catalyst design strategy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
5. Different catalyst used for hydrodeoxygenation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
6. Choice of support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
7. Promoters and their role . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
8. Metallic carbide and nitride catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
9. HDO mechanism over different catalyst materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
10. Catalyst activation and deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
11. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
References . ............................................................................................................ 253

n Corresponding author. Tel.: þ1 306 966 4771; fax: þ1 306 966 4777.
E-mail address: ajay.dalai@usask.ca (A.K. Dalai).

http://dx.doi.org/10.1016/j.rser.2015.03.074
1364-0321/& 2015 Published by Elsevier Ltd.
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
1. Introduction
Globally, the outlook and motivation towards the development and usage
of cleaner and renewable source of energy is growing due to the soaring crude
oil prices, diminishing petroleum resources and environmental health hazards
associated with the emissions from fossil fuels. Increase in production and
consumption of energy is directly related to the growth in population and
economic status of the people. Owing to factors such as capital interests,
fluctuations in oil prices and other geopolitical issues, there is a tremendous
growth in biofuel industry globally [1,2]. Considerable work has been done
focusing on bio-based fuels production from rapeseed oil, soybean oil, palm
oil, karanja oil, waste cooking oil [3,4]. As predicted by International Energy
Agency (IEA), liquid biofuels will dominate the energy sector by 2030.
Table 1 indicates the rise in world energy consumption from 2008 till date
and its future trend [5]. It is seen that there will be a constant rise in the
energy demands in future. Availability of constant energy source at affordable
price is a key factor for a nation's gross domestic product (GDP) [6,7]. Hence
it is essential to find an alternative for the fossil fuel resources to meet the
future energy demands. By 2030, biofuels production is forecasted to reach
6.5 Mb/d in comparison to its production in 2010 (1.8 Mb/d) indicating that
the need and supply are forecasted to increase tremendously in future [8].
Fig. 1a and b indicates the energy consumption in Organization for
Economic Co-operation and Development (OECD) region in 2008 and its
projection for 2035 [5]. Fig. 1c and d indicates the energy consumption in the
Non-OECD region in 2008 and its projection for 2035 respectively. It could
be seen that the energy demands for the Asian countries will rise
tremendously in comparison to Americas and the European Union. From
Table 1 and Fig. 1, it is evident that in future, an overwhelming demand for
alternate fuels will arise and a replacement to fossil fuels is highly essential.
Innovations in technol-ogy, hike in oil prices, employment effects, reduction
in emission of greenhouse gases and continued support from government
through various policies contribute to the rapid growth of biofuels industry.
Fig. 2 a and b represents the growth in biofuel sector from 2009 to 2013
and it confirms the immediate need for alternate fuels across the globe. First
generation fuels primarily involves fossil fuel resources such as coal,
petroleum and natural gases. Depletion in fossil fuel resources and the
environmental issues associated with their usage resulted in the search for
second generation fuels. Production of second generation fuels involves feed
stocks such as corn to obtain bio-ethanol and bio-based fuels. However, most
of the feed sources are edible and they lead to food vs. fuel problem. Third
generation fuel involves usage of feed sources such as lignocellulosic
biomass, waste cooking oil and non-edible vegetable oils.
Recently, technologies such as biomass to liquid fuels (BTL) and
hydrotreatment of vegetable oils to produce green diesel are being focused.
Fig. 3 represents the trend in the growth of biofuel sector. Presently, fossil
fuels and second generation fuels such as biodiesel and bioethanol are being
commercially used and it is very evident that technologies such as BTL and
HVO (hydrotreated vegetable oil) are promising routes to meet the future
energy demands.
Table 1
Past and projected world energy consumption [5].
Year OECDn Non-OECDn World totaln
2008 250 260 510
2015 250 300 550
2020 265 340 605
2025 270 400 670
2030 275 450 725
2035 280 500 780
n quadrillion Btu
241
Methods for upgradation of fuels can be broadly classified into chemical
and physical methods. Chemical upgrading methods includes catalytic
esterification [15] hydrothermal liquefaction, hydrodeoxygenation and
catalytic hydroprocessing [16,17]. Physical upgrading method includes char
removal, hot vapor filtration, solvent addition and extraction of organic acids
[18,19]. In case of hydrothermal liquefaction, the biomass is converted to
fuels and chemicals under supercritical condition, in the presence of water at a
temperature of 350–374 1C and pressure of 20–25 MPa [20]. Inclusive of
hydrodeoxygenation process, other methods such as catalytic cracking
[21,22], emulsification [23,24], steam reforming and esterification [25] have
been investigated for upgradation of fuels. Li et al. [26] reported on
upgradation of bio-oil especially the low-boiling fraction using supercritical
methanol and it was proven to be an efficient method for bio-oil upgradation.
Many other methods such as super-critical method [27,28], pyrolysis [29],
gasification, fisher-tropsch synthesis [30,31], liquefaction and hydrotreating
are also being used to produce liquid fuels [32]. Presently, hydrotreating
process for converting vegetable oils and animal fats into renewable diesel
fuel substitutes is gaining con-siderable importance.
2. Hydrodeoxygenation (HDO) process
During a catalytic hydrotreating reaction, simultaneous removal of sulfur,
nitrogen, oxygen and metals is possible. Factors such as nature of feedstock,
catalyst and process parameters influence the extent of particular reaction.
Hydrodeoxygenation is a process of removing oxygenated compounds from a
molecule usually in the form of water using catalyst such as nickel-
molybdenum supported on alumina and zeolite materials where hydrogen is
used to cleave carbon–carbon or carbon–heteroatom bonds in a molecule.
Oxygen content of the bio-based fuel plays a major role in assessing the fuel
properties. The high oxygen content of vegetable oils (upto 50 wt%) has
adverse effects such as low heating value, thermal and chemical instabilities,
corro-sivity, immiscibility with fossil fuels and increase in tendency towards
polymerization [33].
Hydrodeoxygenation can be a promising process to remove oxygen
content of the fuel thus aiding in the production of bio-based transportation
fuels [34]. Bio-oils obtained from wood and wood residues can be potential
feedstocks for HDO reactions due to their high oxygen content (435 wt%)
and they can be upgraded by physical or chemical methods [35]. Research
efforts to study the chemistry of hydrodeoxygenation of biomass-derived oil
are gaining considerable importance over the last 20 years.
Hydrodeoxygenation process has been reviewed by many groups in the past
(see Table 2). Recently, Mohammad et al. [14] published a review on the
overview of catalytic hydrodeoxygenation to produce paraffin based-biofuels.
They have illustrated the importance of different feed stocks and their
advantages and disadvantages. In the present review, insight into the
chemistry behind the choice of feedstocks, catalyst devel-opment and design
strategies for the better understanding of HDO process are provided.
Hydrodeoxygenation of bio-oil is reported to be the most suitable method to
upgrade bio-oil [36,37]. Industrialization of HDO process was first done by
Neste oil in Porvoo, Finland using vegetable oils as primary feed stocks.
Although HDO is an efficient method to obtain fuel from bio-based feed
stocks, it has not received considerable importance as the petroleum feeds
generally contains 98 wt% carbon and hydrogen, 1.8 wt% sulfur and only 0.1
wt% oxygen [38]. Hydrodeoxygenation of feedstock's that contains
triglyceride produces diesel-like deoxygenated hydrocarbons, with high
cetane number that is fully compatible with petro-diesel [39]. Fig. 4 indicates
the factors affecting the choice of feed source, reaction conditions, product
formation and commercialization of hydrodeox-ygenation process. Out of
these, optimization of catalyst can be the
242 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255

Fig. 1. World energy consumption by country grouping [5].

Fig. 2. World biodiesel production [8].

Table 2
Important reviews on hydrodeoxygenation systems.

S.No Significance Reference

1 Extensive information on the mechanism and kinetics of HDO reactions using different feed stocks [10]
2 Information on bio-oils hydrodeoxygenation and life cycle assessment [11]
3 Information on hydrodeoxygenation of biomass pyrolysis oil [12]
4 Information on hydrodeoxygenation of pyrolysis bio-oil on different catalysts [13]
5 Information on choice of feed stocks and future outlook [14]
6 Information on catalyst design strategy for hydrodeoxygenation of bio-based feedstocks and outlook on bioenergy sector In this study.

most challenging task. Choice of feed stock should be based on the
environmental conditions of the locality. In a province like Saskatch-ewan,
canola oil is available abundantly and it can be a promising feed source. For
efficient design of the hydrodeoxygenation process, choice of catalyst,
optimization of reaction temperature, hydrogen pressure and catalyst loading
is highly essential. Catalyst should be designed to hinder side reactions and
have higher selectivity towards
desired products. Finally, information on supply-demand structure for the
diesel substitute products in a local community and process economics are
mandatory for the commercialization of the hydro-deoxygenation process.
The possible routes for hydrodeoxygenation include direct hydro-
deoxygenation, decarbonylation and/or decarboxylation [40]. In direct
hydrodeoxygenation, organo–oxygen molecules present in feed
stocks
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255 243

Fig. 3. Trend in the growth of biofuel sector [9].

Fig. 4. Overall hydrodeoxygenation reaction system.

react with hydrogen at high temperature (250–400 1C) and pressure (3–10 3. Feed source for hydrodeoxygenation reaction
MPa) and hydrocarbons are obtained as main products.
During direct HDO, the CQO double bond is cleaved initially, resulting in Vegetable oils are ideal sources as they have a chemical structure having
alcohol formation. Furthermore, hydrogenation of C–O bond occurs forming long chain fatty acid with 16-24 atoms of carbon. Choice of feed stocks
alkane. During decarboxylation reaction, oxy-gen is removed as CO 2 by the depends on crop growing pattern of local regions and proper choice of
direct attack on C–C single bond [40]. Reactions involved during feedstock can aid in reduction of tariffs and transportation costs. Soybean oil
hydrodeoxygenation are represented by Eqs. (1) and (2). Eq. (1) is the most is a potential source in United States due to its higher production rate [41].
desired route (direct HDO) as the number of carbons is preserved and the by- Production of rapeseed oil, palm oil and sunflower oil dominates in Europe
product formed is water. and hence, they can be the potential feed stocks for biofuel production in
European nations (Fig. 5). Based on the locality, similar considerations should
be made while choosing a potential feed stock for HDO reactions. Usage of
2.1. Reaction scheme for direct hydrodeoxygenation (Eq. (1)) and renewable bio-based feedstocks as fuel resource have many advantages
decarboxylation (Eq. (2)) pertaining to economic, social and environmental aspects: (i) Stable supply of
H2 raw materials. (ii) Reduction in carbon footprint from the usage of liquid
CH3 ð CH2Þm COOH CH3 ðCH2Þm fuels, and (iii) profitable agricultural economy.
H2 ð1Þ
CH2OH CH3 ð CH2Þm CH3 þH2O
Most of the researchers have used model compounds to investi-gate
H2 CH þCO2 ð2Þ hydrodeoxygenation reactions. Phenol is one of the highly preferred model
CH3 ð CH2Þm COOH CH3 ðCH2Þm
1 3 compounds as it is an oxygenated compound with simple structure [42].
Feeds such as guaiacol [43–48], methyl heptonate [49], sorbitol [50], vanillin
Generally, HDO reactions produce H2O (Direct HDO), CO (decar- [51] and acetic acid [52] have been tried and few papers have reported on
HDO of real feedstocks such as bio-crude [53], vegetable oils [54,55], waste
bonylation) and CO2 (decarboxylation) and desired hydrocarbon compounds
as the products and the product distribution depends on the reaction route and vegetable oil [56], canola oil [57] and bio-oils [58–62]. Specifically, many
catalyst type. works
244 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255

Fig. 5. Feedstocks for hydrodeoxygenation reaction in different regions of the world.

Fig. 6. Biomass to renewable hydrocarbon fuels [71].

have reported the usage of canola [63], palm [64], rapeseed [65], sunflower
[66] and karanja [67] oils as potential feedstocks. Since most of the vegetable
oils are edible, it leads to food vs. fuel problem. In this regard, waste cooking
oil has gained great importance as a feed oil to produce fuel [68,69]. To
improve the social and economic feasibility of bio-based fuels, usage of
affordable and low quality feedstocks are recommended [70].
Production of third generation fuels are mostly based on bio-oils and
vegetable oil. Bio-oils have gained considerable importance as a potential
feed stock for the production of hydrocarbons by catalytic upgradation.
Lignocellulosic biomass is a promising renewable energy source and can be
used to produce bio-based fuel. From the results on characterization of
different biomass, it was con-cluded that pinewood is the most reliable source
owing to its large hemicellulose and cellulose content and high calorific value
[32].
Fig. 6 illustrates the conversion of different biomass to diesel fuel products
[11]. Biomass can be classified as carbohydrates, lignin and fats/oils.
Carbohydrates consist of cellulosic and hemicellulosic materials. Fats
comprises of triglycerides and fatty acids. As name implies, lignin are
basically derived from wood and lignin. Lignin can be hydroprocessed to
form phenols and tar which can be further hydroprocessed to produce
aromatics and naphthalenes [71]. Similarly, sugars from carbohydrates of a
biomass can be converted to sugar alcohols by hydrogenation and further
hydro-processed to yield gasoline products.
Fig. 7 indicates the oil content in seeds and oleic acid content of
different feed oils that can be potentially used as feedstock
for hydrodeoxygenation reaction. As stated earlier, the
choice of feed stock is a factor of regional preference. Due to
abundant availability of canola oil (more than 3.3 million
metric tons) and green seed oil
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255 245

100

(%)
80

in seed/kernel
Oil content in 60

seed/kernel of
different 40
Oil content

feedstocks
20

100
80
(%) content

Oleic acid 60
acid

composition
of different 40
Oleic

feedstocks
20

Fig. 7. Properties of different feed oils [72]. Source:

http://www.chempro.in/fattyacid.htm

in Saskatchewan, canola and green seed (non-edible) canola oil can be the Table 3
potential feed stocks for HDO process in Canadian biofuels industry. Fatty acid composition of canola and greenseed oil (Reproduced with permission from
publisher) [73].
Understanding the reaction mechanisms using real feed stocks can be
Major Fatty acids Methyl ester of Canola oil Methyl ester of Green Seed oil
challenging and HDO studies using model compounds is preferred initially to
elucidate the reaction pathway before eval-uating real feed stocks. Studies on Palmitic 4.21 4.38
HDO of oleic acid can provide useful information on the reaction mechanism Stearic 2.03 1.98
Oleic 62.33 62.74
and can help researchers to design a catalyst that will work efficiently for real
Linoleic 19.13 19.99
feed stocks such as canola oil and waste vegetable oils. Linolenic 9.18 9.60
Eicosenoic 1.26 0.00
Table 3 (reproduced with permission from Elsevier) indicates the fatty Erucic 1.87 1.31
acid composition of canola and green seed oil. Primary fatty acid constituent
is oleic acid. Linoleic and linolenic acids are the next major constituents of
canola and greenseed oil [73].
Greenseed (non-edible) canola oil has high content of chloro-phyll and canola oil are chlorophylls and pheophytins. Due to the high content of
due to its non-edible nature, it is considered as a “waste product” [74,75]. The chlorophyll in greenseed oil, it appears green and it is considered non-edible
major pigments in canola and greenseed making it a potential source for HDO
246 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
reaction to obtain bio-based diesel products. The high chlorophyll content of
green seed canola oil is reported to inhibit the activity of hydrogenation
catalyst. Moreover, the presence of pigments has been reported to have
detrimental effects on the stability of oil and the biodiesel and bleaching of
the oil is proven to remove the pigments [75]. Cerny et al. [76] carried out
hydrodeoxygenation reaction using zeolite USY catalyst and different feed
stocks such as canola oil, palm oil, oleic acid, stearic acid, cis-9-octaden-1-ol
and octadecan-1-ol to study the influence of the nature of carbon-oxygen bond
and the degree of unsaturation present in the reactant [76]. It was concluded
that the usage of saturated alcohols resulted in the formation of the most
desired products (iso-alkane). Using unsaturated feedstocks instead of the
saturated ones resulted in the increased formation of aromatics (410%).
4. Catalyst design strategy
Design of a catalyst can be stated as the systematic application of
available information for the selection of a catalyst in a particular reaction. It
is a challenging task because, accurate and specific methods for catalyst
development and design for specific reaction system are generally scarce and
in most cases, it works on trial and error method. Few authors have employed
computational techniques for accelerated catalyst design [77–83]. Generally,
a variety of catalysts can be predicted to perform well for particular reaction
and can be checked only by experiments. The number of catalyst to be tested
can be reduced by proper application of catalyst design procedure. In catalyst
design, it is often recom-mended to alter the already existing catalyst for a
particular process depending on the needs of the user than to develop an
entirely new catalyst material [84].
Fig. 8 indicates the steps involved in primary design of catalyst. Methods
for designing a totally novel catalyst and altering an available catalyst for
specific purpose differ slightly. Before design-ing a completely novel catalyst,
technical, economic and environ-mental evaluations are mandatory. Catalysts
developed should be technically feasible with no harm to environment and
should be cost-effective. However, if a catalyst needs to be designed for
already existing mechanism, the design could be carried out based on some
chemical grounds. Fig. 9 illustrates the different support materials and active
metals that are being employed for hydro-deoxygenation reaction. Zeolite
materials are used quite extensively as they offer high acidity that enables
cracking of C¼O bond in feed oils and aids hydrogenation. Recently,
mesoporous materials are gaining importance as they offer moderate acidity
and also the required surface area and pore diameter for the reaction of real
feed stocks that are relatively heavier molecules.
Fig. 8. Algorithm for catalyst design [84].
5. Different catalyst used for hydrodeoxygenation process
Many literature have reported on hydrotreating reactions using
conventional metal sulfide catalysts [85] and noble metal catalysts [86].
However, noble metal catalysts are costlier than transitional metal sulfide
catalysts and the cost factor limits the applicability of noble metals as
catalysts for HDO reactions [87]. Table 4 sum-marizes different
hydrodeoxygenation reaction systems that have been investigated over the last
two years.
Transition metallic sulfides of nickel, cobalt and molybdenum are proven
to be efficient catalysts for hydrotreating reactions such as
hydrodesulfurization (C–S) and hydrodenitrogenation (C–N). Hence, it can
be assumed that the same active metals could work for hydro-deoxygenation
(C–O) reactions. Sulfidation process is carried out at high temperature (280–
350 1C) using hydrogen sulfide (H2S) or carbon disulfide (CS2). Senol et al.
[88] reported that the usage of H2S as sulphiding agent is more beneficial than
CS2 due to decrease in hydrogen consumption and coke formation. High
oxygen (430 wt%) and low sulfur content (o3 wt%) of the feed (vegetable oil)
can cause oxidation of the active catalyst phase and thus deactivating the
sulfide catalyst. In Canada, diesel fuel should have less than 15 ppm of sulfur
content for transportation usage (Canadian Environmental Protection Act,
1999). Hydrotreatment of fossil fuels and model compounds have been
studied and it was shown that non-sulphided catalysts can be successful in
removing many impurities such as oxygen, sulfur and nitrogen. Furimsky [89]
emphasized that reduced catalysts have strong tendency to remove impurities
(nitrogen, sulfur and oxygen) by hydrotreating process.
Li and Huber [90] studied on aqueous-phase hydrodeoxygena-tion of
sorbitol using Pt/SiO2–Al2O3 catalyst and have concluded that dehydration
reaction occurs on the bronsted acid sites of the catalyst. Hydrogenation
reaction is exothermic and hence favorable at low temperature and in
conventional processes, temperature range of 573–618 K and hydrogen
partial pressure in the range of 3.5–6.8 MPa are preferred. Severity of
operating conditions depends on the nature of the feed. Especially, heavier
feed requires high temperature and pressure for proper hydrogenation. Zhao et
al. [91] have performed hydrodeoxygenation of phenols to cycloalkanes using
dual-functional catalyst system (Pd/C and H 3PO4). They have studied the
influence of catalyst support, pH value of aqueous solution, metal sites, and
temperature on the HDO activity. In HDO reactions of vegetable oils or bio-
oils, preference towards hydro-genolysis of carboxylic groups or carbonyl
groups is high in comparison to saturation of C–C bonds as the latter can
reduce the products octane number [92]. Bykova et al. [45] have used nickel
based sol–gel catalyst for the hydrodeoxygenation of guaia-col. Different
loadings of nickel and copper on stabilizing compo-nents such as γ-Al2O3,
CeO2, ZrO2, SiO2 and La2O3 were employed to
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255 247

Fig. 9. Catalyst development for hydrodeoxygenation reaction.

Table 4
Summary on the recent studies of different hydrodeoxygenation reaction systems.

S. Model compound/feed Catalyst system Max. conversion/products References

No
Active Support material
metal

1 Dibenzofuran NiP – 99% (T ¼300 1C, PH2 ¼3 MPa) [122]

2 Phenol, cresols, guaiacol and Platinum Zeolite-beta 99% (T ¼180 1C, PH2 ¼5 MPa) [123]
eugenol (Pt)
3 Soybean oil Pt, Ni, Co– Al2O3, SiO2–Al2O3 95% (T ¼400 1C, PH2 ¼9.2 MPa) [124]
4 Jatropha oil Mo 1
99.85% (T¼360 1C, P¼3.3 MPa, LHSV¼1.0 h ) [125]
Ni-HPW Al2O3
5 Methyl ester Ni, Co SBA-15, Al–SBA-15 98% (C17 paraffin's, Cat-Ni/Al–SBA-15; T ¼340 1C, PH2 ¼3 MPa) [126]
6 Guaiacol Fe SiO2, Activated Carbon 100% (10% Fe/AC, T¼673 K, P¼1 atm) [99]
7 Bio-oil Ni ZSM-5, Al2O3 91.8%(T¼240 1C, PH2 ¼4.0 MPa, 10 wt% Ni/ZSM-5) [103]
8 Guaiacol Ni, Ni–Cu ZrO2–SiO2 100% (T¼300 1C, PH2 ¼5 MPa, t¼8 h, NiCu (5 wt%)/ZrO2–SiO2) [127]
9 Methyl isobutyl ketone Pt, Pd, Cu SiO2, C, HZSM-5 100% (T¼100 1C, t ¼1 h, 0.5% Pt/HZSM-5) [128]
10 Jatropha oil Co–Mo Al2O3 99.99% (T¼360 1C, PH2 ¼80 bar) [129]
11 m-Cresol Ga H-Beta, ZSM-5, HZSM-5 and 84.52% (T¼450 1C, PH2 ¼1 atm, Ga (3 wt%)/H-Beta). Conversion reached [130]
Silica 95% when T ¼550 1C
13 Guaiacol Ni–Cu Al2O3, SiO2, CeO2–ZrO2, ZrO2– 97.5% (T ¼320, P¼17 MPa, t¼1 h, Ni(55 wt% )SiO2 [45]
SiO2–Al2O3
14 Propanoic acid Ru, Ru– ZrO2 95% (T ¼210 1C, P¼6.4 MPa, Mo/Ru¼0.2, Ru–Mo/ZrO2) [131]
15 Oxygenates in aq. Fischer Mo 1
94.4% (T ¼200 1C, PH2 ¼9.8 MPa, LHSV¼3.0 h , Ru/TiO2)
Ru ZrO2, TiO2, SiO2, Al2O3 [132]
Tropsch process
Pt γ-Al2O3, mixed silica alumina, 11.9% (T¼225 1C, PH2 ¼29 bar, Pt (0.8 wt%)/Al2O3 [133]
16 Glycerol
SiO2

investigate the HDO reaction. Nickel based sol–gel catalysts have been thermally more stable and less acidic than γ-Al2O3 and this helps in reduced
reported to outperform the conventional sulfide Ni(Mo), Co (Mo) and noble coke formation. The loadings of nickel and copper were changed and their
metal catalysts owing to factors such as higher stability towards coke effects on hydrodeoxygenation rate were mon-itored. Leaching levels and
formation, low cost, stability towards leach-ing of active components. carbon deposition were lowest when the nickel loading was maximum (16 wt
Catalyst with 55.4 wt% of nickel with no copper loading stabilized using SiO 2 %) indicating that usage of promoter's aid in increasing the resistance towards
2 coking. Lee et al. [94] studied the hydrogenation of model (oxygenated) com-
is reported to have higher surface area (ABET ¼216 m /g; d¼20 Å) than the
2 pounds such as acetaldehyde, xylose and furfural using Palladium (Pd),
other synthesized catalysts (66–142 m /g). This could be attributed to the
Platinum (Pt), Ruthenium (Ru), Rhodium (Rh), Nickel (Ni) and Cobalt (Co)
blocking of some of the pores during the loading of copper. Presence of
copper aids in the reduction of nickel oxide at lower temperature and hinders supported on Alumina. Moreover, they used the same catalysts to investigate
tetrahydrofurfuryl alcohol hydrogenolysis. From their results, it was
coke formation. Nickel supported on SiO 2 (without copper) gave better
concluded that Rh seems to outperform all the other mono-metallic systems
conversion of guaiacol (97.5%) and HDO (97.3%). How-ever, degree of
for hydrogenation reaction. Additionally, from their studies on
coking was high in comparison to other catalysts with copper loading. One
specialty about this study is the use of pure guaiacol without any solvent. hydrogenolysis of THFA and Xylitol, it was confirmed that Rh is a promising
active metal for both hydrogenation of CQO and CQC bond and
hydrogenolysis of C–C bond. However, Pt, Ni and Co are reported to be more
suitable for
Ardiyanti et al. [93] used bimetallic Ni–Cu supported on δ-Al2O3
catalysts for the hydrodeoxygenation of fast-pyrolysis oil. δ-Al2O3 is
248 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
hydrogenolysis of C–O–C bond. During the hydrogenolysis of THFA, 20 wt
% of Ni/Al2O3 is reported to give a conversion of 17.3% with 0% selectivity
towards 1,2-pentanediol and 59.2% selectivity to 1, 5 pen-tanediol. However,
3 wt% Pt/Al2O3 gave 9.3% conversion and 38.9% selectivity towards 1,2-
pentanediol and 0% selectivity to 1, 5 penta-nediol. Echeandia et al. [95]
studied on the synergetic effects of tungsten precursors in the
hydrodeoxygenation of phenol over Ni–W supported on active carbon. It was
stated that tungsten from heteropolyacids (HPA) performed better and
activated carbon gave better conversion than the conventional alumina
support. Chances of methanation are high during HDO reactions. CO and
CO2 produced by HDO reactions through decarbonylation and
decarboxylation can react with H2 (water–gas shift and methanation
reactions) to form methane. Methane is a worse green house gas than CO2 and
hence this reaction is highly undesirable. Chen et al. [134] studied on the
effect of Ni/Mo ratio on deoxygenation of model compound (methyl laurate)
using NiMo phosphide catalysts. Electron transfer between the promote and
the active metal plays a vital role in the hydro-deoxygenation activity and the
transfer is governed by the Ni/Mo ratio in active phase. During phosphidation
of catalyst presence of MoNiP2 is confirmed by XPS analysis and it is due to
the incorpora-tion of Mo atoms into Ni 2P increasing the chemical binding of
Ni-Mo species. It is also reported in the same paper that occurrence of
MoNiP2 phase is beneficial as it aids the catalytic activity of the NiMo
phosphide catalyst. Catalyst for HDO reaction should be particularly designed
so that these undesired side reactions are inhibited.
6. Choice of support
Choice of support is also a key factor for determining the
hydrodeoxygenation activity of different catalysts. The most com-mon and
conventional support is γ-Al2O3 [96]. γ-Al2O3 has many beneficial properties
such as high stability and moderate/slight acidity. However, catalyst
deactivation due to coke formation is a major problem especially with the use
of alumina support. Alter-native materials such as SiO 2, active carbon, TiO2,
ZrO2, Nb2O5, zeolites and various metal oxides were used in HDO reactions
[97]. Hydrodeoxygenation reactions have been traditionally carried out using
moderate-highly acidic support materials such as oxides of alumina, silica,
zirconia and all these materials have high ionic potential. Support materials
such as calcia and magnesia are basic materials with low ionic potential and
usage of basic supports and thoria (acidic support) are scarce with respect to
HDO reactions. One interesting fact about using activated carbon as support
is that, their activity depends on the preparation method and hence, tailoring
of their activity is a possibility. This unique property can make activated
carbon a suitable choice as a support material for HDO reactions. Low-
temperature carbons have acidic hydrophilic surface while high-temperature
carbons tend to have basic and hydrophobic surfaces.
Deoxygenation of methyl ester to olefins is shown in Fig. 10. Reaction
pathway (a) is desired which involves conversion of methyl ester to α-olefin
[98]. Chiappero et al. [98] have reported the occurrence of both the desired
and undesired pathways using PtSnK supported on silica. However,
selectivity towards formation of α-olefin was reported to be higher (450%)
compared to olefin isomers.
Bui et al. [43] compared the support effects (zirconia, titania and Al 2O3)
for CoMoS catalyst on the hydrodeoxygenation of guaiacol. Guaiacol is a
model compound used to represent lignin. It was concluded that the
performance of zirconia support was better than titania and γ-Al2O3 in terms
of HDO conversion and product selectiv-ity. NiMo supported on ZrO 2, TiO2
and γ-Al2O3 were characterized using Raman spectroscopy to confirm the
occurrence of desired metal-oxide species. Zirconia support offers both basic
and acidic nature; basic nature of the support material helps to reduce coke
formation
Removal of CO, CO2 ,CH4
O
a
O
b Olefin
Methyl Ester
Olefin isomer
Fig. 10. HDO Pathway for methyl ester (a) desirable and (b) undesirable pathways [98]
(Reproduced with permission from publisher).
and acidic nature helps to aid hydrogenation and subsequent C (sp2)–O bond
cleavage and deoxygenation reactions. Olcese et al. [99] have compared the
performance of Fe/SiO and Fe/Activated carbon for hydrodeoxygenation of
guaiacol. For the same iron loading, the guaiacol conversion was higher with
the usage of silica support than activated carbon. However, the selectivity
towards desired product was higher with the usage of activated carbon
support material.
Catalyst design for HDO reactions can be done by altering the host lattice
(support) and seeing the influence on the guest metal ion on catalytic activity.
When the host lattice changes, the inter-action and the co-ordination
environment of the guest ion changes. Alternatively, studies can be done by
keeping the host lattice same and varying the concentration and/or nature of
the guest ion (change in the active metals). Primary advantage of using porous
support is that the extent of availability of active metal for catalytic reactions
can be controlled. Preparation methods can govern the diffusion limitations to
obtain well-distributed metal catalysts.
Molybdenum forms polymolybdate species at any loading on silica
supports due to the similarity in isoelectric points of silica and MoO 3.
Generally active metals such as Ni or Co are used and Ni has better activity
towards hydrogenation than Co. A lower activity towards HDO can be
directly linked to lower acidity of the catalyst support materials. Nava et al.
[100] also stated that catalyst acidity and extent of coke formation have no
correlation which seems contradicting to their statement where lower acidic
strength of MCM-41 was related to the lower coke formation in comparison
to zeolite which has considerable higher acidity.
Influence of sulfidation rate has lesser influence than the acidity of support.
Hence, degree of carbidation or nitridation of exposed active metal species
may not play a vital role in HDO activity in comparison to the acidity of the
support. In comparing the supports SBA-15, SBA-16, MCM-41 and DMS-1,
Nava et al. [100] have stated that HDO selectivity towards desired products
(paraffin's and olefins) was better in DMS-1 support material. Formation of
Bronsted acid sites is important for hydrogenolysis during HDO reactions and
the formation depends on silanol groups structure when silica–alumina is
used as the support material. Incorporation of aluminum increases the catalyst
acid strength. As incorporation of aluminum occurs near silanol groups, the
OH groups on surfaces acts as bronsted acid sites. It is widely accepted that
activity of catalyst for hydrogenation can be increased by promoting the
acidity of catalyst by introduction of acidic solvents and/or supports.
Kubicka et al. [101] studied on the deoxygenation of rapeseed oil using
support material such as SiO2, TiO2 and Al2O3 using nickel (3.3 wt%) and
molybdenum (15 wt%) as catalyst. HDO reactions were performed at a
temperature range of 260–300 1C and hydrogen pressure maintained at 3.5
MPa. It can be observed from their work that product selectivity depends on
the nature of support material to a considerable extent. TiO 2 supported NiMo
catalyst exhibited high selectivity towards hydrodeoxygenatlon product in
comparison to other support materials. In the case of TiO 2 support, the
active phase was not dispersed well and the active phase
cluster size was high.
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
However, SiO2 exhibited better dispersion of active phase in compar-ison to
Al2O3 and TiO2 and this well dispersion is reported to be the main reason for
the preferential decarboxylation over SiO 2. From this work, it is clearly
observed that metal-support interaction and the support properties plays a
crucial role in the choice of reaction pathway and also the formation of
desired products.
Yang et al. [102] studied on the hydrodeoxygenation of anisole over
nickel supported on materials such as carbon, γ-Al2O3, SBA-14, Al– SBA-
15, CeO2, TiO2 in a fixed bed reactor system. Major products formed by the
hydrodeoxygenation of anisole are hexane, cyclohex-ane, benzene and
toluene. Conversion of anisole and selectivity towards products differed
significantly depending on the different supports. In the case of Al–SBA-15
and SBA-15, the conversion of anisole showed less difference (o3%).
However, the selectivity towards the products differed significantly (45%).
Conversion and selectivity were reported at two reaction temperatures (290
1 1
1C and 310 1C) and LHSV (20.4 h and 81.6 h ). It was reported that, at
higher temperature (310 1C), the selectivity towards hexane was high
1 produce minimum amount of coke in comparison to strongly acidic support
(LHSV-20.4 h ; Cat: Ni/SBA-15; Shexane¼40%). At a temperature of 290
1C, the selectivity was 22% at the same process conditions. Zhang et al. [103]
synthesized nickel (different loadings) supported on ZSM-5 and Al2O3. ZSM-
5 represents a highly acidic support material, while Al2O3 represents
moderately acidic support material. Conversion of bio-oil using nickel
supported on ZSM-5 and Al2O3 (10 wt%) were 91.8% and 20.9%
respectively. However, characterization of the catalyst materials to analyze
the metal-support interaction is essential to support the conclusions
substantially. Information on active metallic surface area and metal dispersion
is recommended to help find the justification for the significant difference in
the conversion of bio-oil. Zhao et al. [104] synthesized nickel supported on
HZSM-5 and Al2O3– HZSM-5 and evaluated them for the
hydrodeoxygenation of phenol. The purpose of this study was to understand
the influence of Al2O3 binder on the Ni/HZSM-5 catalyzed
hydrodeoxygenation of phenol. Catalyst samples were characterized using
XRD, TEM, lR, TPR, EXAFS and XANES and it was concluded that, Ni
supported on Al2O3–HZSM-5 had higher concentration of nickel atoms in
comparison to Ni/HZSM-5. Moreover, usage of binder like Al2O3, resulted in
strong and higher adsorption capacity of reactant molecules on Al 2O3 leading
to better product conversion. Catalyst deactivation due to sintering is also
reduced by the usage of binders. Nickel oxide forms a strong chemical bond
with the binder (NiO–Al2O3) and forms ‘pseudo spinels'. This strong
chemical interaction makes the reduction of NiO/Al 2O3–HZSM-5 tougher
than NiO/HZSM-5 as confirmed from their TPR results.
Over the years, usages of basic support materials have not gained
considerable attention. Acid–base interaction between the basic support and
the metal solution can promote dispersion of active metal species on catalyst
support. Secondly, coke formation can be inhibited by the basic nature of the
support. Literature on hydrodeoxygenation reaction using MgO-supported
catalysts are generally scarce. Yang et al. [53] studied on hydrodeoxygenation
of bio-crude using phenol as model compound in super-critical hexane at
300–450 1C and hydrogen pressure of 5.0 MPa using sulfided CoMo/MgO
and CoMoP/MgO catalyst. It was concluded that the basic support is active
for hydrodeoxygenation reaction only at reaction temperature greater than 350
1C. XPS analysis was performed on fresh and spent CoMo and CoMoP
catalysts. It was found that coke formation on the MgO supported catalyst
was considerably less (o20%). Since, the bond energy of CQO is high in fatty
acids, support materials with moderate to high acidity are generally preferred.
However, cracking reactions renders products with less carbon number. One
of the major roles of support is adsorption of reactant molecules in close
proximity to active metal particles. During HDO, H 2 molecules adsorb on
active metal and are supplied to the reacting molecule by spill-over
mechanism. Adsorp-tion of the reacting molecule can vary depending on the
acid–base nature of the support material and this affects selectivity towards
249
certain products. Velu et al. [105] have stated that phenol (popular model
compound for HDO reaction) adsorbs in non-planar fashion on basic supports
and it adsorbs in co-planar fashion with respect to the surface on acidic
supports. Support materials such as CeO2 and ZrO2 are gaining importance
owing to their main advantages like higher thermal stability, better dispersion
of metals, ability to store oxygen and redox properties.
Hydrodeoxygenation of bio-based feedstocks deals with bulkier molecules
and hence support materials such as MCM-41 which has high surface area in
2
the range of 600–1000 m /g and homogenous pore diameters from 1.5 to 10
nm are highly recommended. Acidity of support material plays a crucial role
in degree of coke formation. Support materials such as zeolites are highly
acidic and can lead to higher degree of coke formation. However, moderate
acidity is essential for the breaking of carboxylic acid group when vegetable
oils are used as feed stock during hydrodeoxygenation. Using support
material such as MCM-41 which has lower strength of acidic OH groups
materials. SBA-15 can be an effective support for hydrotreating reactions.
SBA-15 with hexagonal pores in a 2D array has thicker walls (3–9 nm) than
MCM-41 and this makes them thermally stable than MCM-41 [106].
Belonging to the same series, SBA-16 was synthesized and scarcely used in
hydrotreating reactions. SBA-16 is cubic cage-structured mesoporous silica
mate-rial and it can be a promising support for hydrodeoxygenation of bio-
based oils because, it has body-centered structure in which each mesopore is
connected to eight neighboring mesopores and this allows easier diffusion of
bulkier molecules into pores [100]. Nava et al. [100] published a significant
article to report on usage of disordered mesoporous silica (DMS-1) having
2
surface area in range of 600–1000 m /g.
Wide range of acidic, neutral and basic supports have been used for
hydrodeoxygenation reactions. Most of the studies have focused on using
acidic (ZrO2) or moderately acidic supports such as Al 2O3 and SiO2. Usage of
neutral supports such as SBA-15, MCM-41 and KIT-6 are gaining
importance. Overall, studies on basic support are scarce and this is due to
their lower activity at temperatures less than 350 1C. On a commercial scale,
carrying out reactions at reaction temperatures above 350 1C may not be
viable owing to the huge energy supply. Acidic supports have the potential to
break the CQO bond in fatty acids and can perform hydrodeoxygenation at
temperatures less than 350 1C. However, cracking and coke formation are
crucial parameters that need to be addressed. Other parameter that should be
considered during the choice of support is its porosity as the real feed stocks
such as vegetable oils are bulky molecules, and porosity of support material
plays a crucial role for the efficient HDO of real feed stocks.
Support material which offers intermediate metal–oxygen bond strength
are considered to be the best support materials. Strong metal–oxygen bonding
causes difficulty in the creation of oxygen vacant sites on the catalyst material
to adsorb oxygen containing compounds. Weak metal–oxygen bonding makes
the abstraction of oxygen from the feed challenging [13]. Basic support offers
higher resistance towards sintering and deactivation, but the conversion and
hydrodeoxygenation rate are reported to be less in comparison to acidic
support materials. Though acidic support materials offer higher conversions,
they suffer from deactivation significantly. Conclusively, moderate to slightly
acidic supports such as TiO2, ZrO2 and Al2O3 have gained great importance
and their usage is highly recommended for hydrodeoxygenation systems.
7. Promoters and their role
Over the years, cobalt, tungsten and nickel have been used as promoters
for hydrotreating reactions [107,108]. Usage of bimetallic
250 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
or multi-metallic catalysts is gaining considerable importance as they show
two distinct effects: i) ‘Ensemble effect’ caused by the influence of geometry
and ii.) ‘Ligand effect’ due to the influence of electronic interaction [84].
Usages of bimetallic catalysts are reported to show better catalytic activity
than single metal catalysts. Amount of promoter used is a crucial parameter
and as reported by [109], excess usage of Ni (promoter) can possible result in
formation of Ni–γ-Al2O3 (Promoter–support interaction) and thus lessening
the availability of active sites (Ni–Mo–S) for catalytic reactions. Excess
promoters can accumulate on the desired MoS2 phase and make the catalyst
inactive. In hydrotreating reactions using molyb-denum sulfide catalysts,
promoters increases the catalytic activity of the active metal used by donating
electrons to the metal, thus weakening the metal-S bond. Similar trend can be
assumed for the metallic carbide and nitride catalysts.
At lower temperature (80–100 K), the promoter Ni atoms remain in
metallic state at the top of Mo substrate and is not able to remove S from Mo
to form NiSy state. At higher temperatures of 600 K, metal and substrate
intermix significantly and it is essential for the formation of NiMoS x complex
in the case of metallic sulfide catalyst. Similar effects can be proposed for the
carbide and nitride catalysts. From the same paper, it can be observed that,
adding promoters such as nickel reduces the binding energy of Mo 3d levels
for MoSx catalyst. In Fermi levels located in valence regions, availability of
density of states (DOS) rises and this change is one of the major reason for
the increase in catalytic activity when doping with a promoter in comparison
to catalytic activity without a promoter.
Use of promoters such as boron, creates new Lewis and Bronsted acid
sites, increasing the overall acidity of the catalyst material. Addition of
phosphorous also has similar effect as boron [110]. Presence of boron alters
the oxide structure of molybdenum. It helps in increasing the octahedral
2
molybdates density in comparison to tetrahedral MoO 4 species and thus
promoting the activity of the catalyst. Moreover, promoters alter the catalyst
geometry by increasing the number of stacks. Usage of promoters such as
cobalt (Co) and lanthanum (La) were reported to increase selectivity of
catalyst (490%) towards oxygen free products [111].
Romero et al. [112] studied on the hydrodeoxygenation of 2-ethylphenol
using unpromoted Mo/Al2O3, CoMo/Al2O3 and NiMo/ Al2O3 catalysts. It
was concluded that using promoters increased the deoxygenation rate.
Moreover, nickel was reported to promote only hydrogenation, but cobalt
promoted both hydrogenation and direct deoxygenation reaction. From their
results, it could be seen than the incorportation of active metal and the
promoter seems to increase the BET surface area of the support material.
Generally, clogging of pores occurs while loading and the increase in the BET
area seems to be quite contradicting. Yang et al. [53] have stated that activity
of MoS2 based catalysts for hydroprocesses can be improved especially on
HDN by doping of phosphorous that act as promoter. Villarroel et al. [113]
studied on the promotional effects of promoters like Mn, Fe, Co, Ni, Cu and
Zn through spillover hydrogen for hydrodesulphurization reaction. The
promoters are reported to favor the migration of hydrogen spillover. One of
the major factors that need to be considered during the choice of promoter is
promoter–support interaction. Based on the catalyst activation conditions and
the oxidation state of the metal, some promoters (ex. Nickel) form strong
chemical bond with support and this reduces the activity of the catalyst.
8. Metallic carbide and nitride catalysts
Review by Furimsky [89] illustrates many important properties of metallic
carbide and nitride catalysts. Metallic carbides and nitrides of transition
metals such as molybdenum and nickel have been proven to be beneficial for
hydrogenation and deoxygenation reactions. Hydrodeoxygenation activity of
metallic carbide or
nitride catalyst will depend on factors such as the anionic vacancies that are
generated by catalyst reduction and the Bronsted acidity of the support
material. Noble catalyst are generally expensive and this causes limitations in
their usage for hydrodeoxygentaion reactions [87]. Preparation method for
catalysts plays a crucial role as structure properties and chemical composition
of catalysts determines the performance of catalysts.
Temperature programmed reduction (TPR) method developed by Lee et
al. [114] is the most prominent and used method for synthesiz-ing metallic
carbide catalyst and carburization temperature is generally within 973 K and
1000 K. The oxide precursors are converted to the active form (sulfide,
carbide, phosphide or nitride) before being used in hydrodeoxygenation of
biobased liquid feedstocks. Reports on usage of phosphide catalyst for the
hydrodeoxygenation reaction is very scarce and the reason is still unknown
[115,116]. Catalyst obtained from in-situ decomposition showed better
hydrogenation activity than catalysts obtained by ex-situ decomposition for
the hydrodesulfurization of dibenzothiphene. In hydrotreating reactions, well
dispersed catalysts can perform better than crystalline catalysts. Degree of
stacking has a crucial effect on the catalytic performance and Yang et al.
[117] have reported that selectivity between hydrogenolysis and
hydrogenation can be affected by the extent of stacking.
Factors such as rate of heating, nitridation temperature and its duration,
hydrocarbon/H2 ratio, carbon and metals sources should be addressed during
development of novel catalysts. Surface carbon deposition is a major problem
during the preparation of carbide catalysts, if temperature and carburization
conditions are not chosen. Passivation of metallic carbide and nitride catalysts
is important as they are pyrophoric. Usually, 1 % O2 is used for the
passivation process [89]. In the past, metal nitride catalysts have attracted lot
of attention. During the catalyst activation, pure NH 3 or ammonia and helium
mixture are used. Mixture of methane and hydrogen or ethane and hydrogen
are used for catalyst reduction and carburization. Extent of carburization
affected the active site density on Mo 2C and hydrocarbon content in H2
mixture influences carbide structure [89,114,118].
Carbidation or nitridation of metal–oxygen species will produce water
similar to the production of ambient water during sulfidation of metal–oxygen
species. Presence of water weakens the metal–oxygen bond and decreases the
activation energy for carbidation or nitrida-tion and it also provides more
surface protons resulting in lower activation energy for Bronsted site assisted
sulfidation. Transition metals can be made to resemble noble metals in terms
of physico-chemical properties by means of reduction
(carburization/nitridation). Since group VI metal carbides and nitrides
resemble noble metals, they have fewer tendencies towards recarburization in
comparison to carbides and nitrides of Group V metals. Molybdenum
carbides have hexagonal close-packed structure whereas Molybdenum
nitrides have body-centered cubic crystal structure.
Interaction between Ni–S species has adverse effect on reactiv-ity of
active metal (Nickel). Similarly, in case of hydrodeoxygena-tion reaction
systems, it can be assumed that interaction between Ni–O species should be
lessened. On sites with active metals, cleavage of C–C bond occurs while
acid sites favours cleavage of C– O bonds occurs by dehydration reactions
[119]. Frauwallner et al.
[120] synthesized molybdenum carbide catalyst using toluene as the carbon
source. Raman spectroscopic analysis of Molybdenum oxides (MoO 3 and
MoO2) shows sharp nature of the peak indicat-ing that the catalyst had a
highly ordered structure. During the reduction of precursor material (MoO 3),
the removal of oxygen results in generation of oxygen vacancies (anionic
vacancies). Mo2C and MoO3 were compared based on Raman shift in the
600–1100 cm 1 region of Raman spectroscopy. Broadening of peaks was
observed in the case of metallic carbide catalysts indicating that there is
decrease in crystallinity as the concentra-tion of oxygen vacancies is
increased.
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255 251

Calcination at high temperature can cause collapse of ordered mesoporous
structure. It should be noted that catalytic performance of transition or noble
metals are better with mesoporous oxide support with high surface area in
comparison to commercial supports with low surface area and the former can
offer higher degree of dispersion with increased stability of metal particles
upon calcination and reduction. The
+H
(1) 2
term high-low surface area seems to be relative and clear and specific range of
surface area for enhanced HDO activity is yet to be documented. Depending
on the catalyst loading and calcination temperature, the catalyst precursor
exists in different forms: (i). tetrahedral species in isolated state, (ii).
polymolybdates or (iii). Oxides of molybdenum when molybdenum is used as
active metal. HDS activity of a sulphided catalyst is highly dependent on the
2
surface concentration of S . Hence, similar correlation can be observed in
3
case of metallic nitrides (N ) and carbide catalysts.

RCOR+CO 2 RCHOHR
+RCOOH RCOOCH R
2
RCOOH (2) +H2 RCH2OH
RCHO 9. HDO mechanism over different catalyst materials
+H2 RCH3

(3) -H2O Understanding the reaction mechanism using model compounds such as
+H2
/CO CH4 oleic acid and stearic acid will help us to develop efficient catalysts for real
R+CO2
feed stocks. HDO of carboxylic acid proceeds by three routes: Route 1
Fig. 11. Main reaction pathways for HDO of carboxylic acids, R represents alkyl groups [13]
(Reproduced with permission from publisher). involves ketonization by the cleavage of C–O bond

Catalyst HDO reaction mechanism

Noble metal catalysts
(Mechanism a)

Noble metal catalysts

(Mechanism b)

Transition metallic
phosphide catalysts

Transition metallic
carbide and nitride
catalysts
(M1: unsaturated
metals, M2: C or N)

Fig. 12. HDO mechanism over different catalyst materials [13].

Note: Blue-Metal 1; Brown-Metal 2.
252 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
forming ketones which undergoes further hydrogenation to produce alcohols.
Alcohols undergo further deoxygenation (dehydration and hydrogenation) to
produce paraffins. Route 2 involves the formation of aldehyde through
hydrogenolysis by the C–O bond cleavage forming alcohols. Alcohols can
undergo dehydration and hydrogenation to yield alkanes or they can react
with the feed (carboxylic acids) forming esters. Route 3 involves the breaking
of C–C bond forming alkanes. CO2 and CO are formed as byproducts through
decarboxylation and decarbonylation reactions respectively (Fig. 11).
Based on some earlier works, He and Wang [13] proposed HDO
mechanism over noble metal supported catalysts, transition metal-lic
phosphide, carbide and nitride catalysts (Fig. 12). With publish-er’s
permission, Fig. 11 was reproduced from He and Wang [13] and with
publisher’s permission, Fig. 12 was redrawn based on the illustrations
presented in the same paper. In their review work, they have addressed on the
influence of catalyst properties on the hydrodeoxygenation of pyrolysis bio-
oils. Over the noble metal catalysts, the reaction mechanism can proceed in
two ways (mechanism a and b). In mechanism a, hydrogen is adsorbed on the
noble metal sites and the feed compound gets adsorbed and activated on
either noble metal sites or the metal-support interface. Adsorbed hydrogen
reacts with the adsorbed feed compound by the spill-over mechanism and
forms deoxygenated products and H 2O by the cleavage of C–O bond.
Mechanism (b) occurs in the case of reducible metal oxide species. When the
metal oxides are reduced in the presence of H 2, oxygen vacancies are created
and the vacancies are filled by the oxygen from the reacting molecules.
δ þ
M and Bronsted sites acts as the main active phases for
hydrodeoxygenation reaction using transition metallic phosphide catalysts.
Activation of oxygen containing compounds and the adsorbed hydrogen
δ þ
occurs on the M sites and the adsorbed feed compound reacts with H
δ þ
atoms from M sites and Bronsted PO– H sites to form deoxygenated
products.
In the case of metallic nitride catalysts, activity depends on metal
oxidations state and the N deficiency. Transition metallic carbide catalysts
offers the permeation of carbon atoms and it increases the d-band electron
density by lengthening the distance of metal–metal species of transition
metals.
Kim et al. [50] studied on the hydrodeoxygenation of sorbitol using Pt/Zr
phosphate and Pt–ReOx/C catalyst and analyzed the influence of the support
material on extent of hydrodeoxygenation. It is reported that Pt–ReOx/C
catalyst shower 34 times higher reaction rate than Pt/Zr-P. Over the carbon
surface, the Pt particles had a less diameter (1.2 nm) in comparison to
zirconium phosphate
Fig. 13. Probable structure of Pt/Zr-P and Pt–ReOx/C under reaction conditions [50] (Reproduced with
surface (26 nm). Particle size of the active metal plays a crucial role in
providing active sites for the adsorption of the reactant mole-cules. Activity
of Pt/Zr-P for C–O vs. C–C bond cleavage is reported to be higher than Pt–
ReOx/C catalyst. From the diagram (Fig. 13), it can be seen that the acid sites
at the location of Pt/Zr-P species are separated from the sites where metal Pt
sites are present. However, acid sites on Pt–ReOx/C are in close proximity to
metal Pt sites. Acid sites’ location in relation to metal site is important to
determine catalyst performance [50]. As a conclusion, it could be stated that,
for better C–O bond cleavage, the catalyst should be designed in such a way
that the metal site and acid site are atomically separated (Fig. 13).
Increase in acidity aids hydrogenolysis reaction which is very crucial for
breaking the C–O bond in bio-based oils/feedstocks during
hydrodeoxygenation. As stated by Ferdous et al. [109], HDS, HDN or HDO
activity depend on the extent of dispersion of active metal on the support
material and also on the state of the active metal phase. Energies involved in
the bonding of C–O, C–N and C–S is essential to design the catalyst. The
CQO bond is stronger (745 kJ/mole) than CQN (615 kJ/mole) and C–S bonds
(477 kJ/mol). In case of single bonds, the energy of the bonds are as follows
C–O: 351 kJ/mole; C–N: 276 kJ/mole; C–S: 255 kJ/mole
All these values indicate that the order of difficulty in hydro-treating can
be arranged as follows: HDO4HDN4HDS. Little information is available on
the difficulty level of hydrodemetalli-zation reactions.
10. Catalyst activation and deactivation
Rate of hydroprocessing reaction depends on active hydrogen available on
catalyst surface [89]. Hydrogen activation happens at the metallic sites and
activation process can be hindered if the adsorp-tion and hydrogen activation
is slower than the adsorption rate of reactant molecules and product must
desorb rapidly so that another cycle of adsorption of reactant–activation of
molecules–transfer to active site–desorption of products occurs. Information
available on metal carbides is less than metal nitrides and this may be due to
the complex procedure involved with the preparation of metal carbides.
According to Furimsky [89], “Molybdenum carbides and nitrides are
capable of adsorbing, activating and transferring active surface hydrogen to
reactant molecules. Presence of both metallic molybde-num and oxygen in the
catalyst surface will modify hydrogen adsorption/activation compared with
the pure carbides and nitrides.
permission from publisher).
 N. Arun et al. / Renewable and Sustainable Energy Reviews 48 (2015) 240–255
The crystal structure of metal carbides and nitrides is favorable for the
migration of active hydrogen from the surface to sub-surface. However, the
complete saturation of the sub-surface with hydrogen may prevent loss of the
surface hydrogen due to its migration to the sub-surface. Generally, promoted
(bi-metal) carbides and nitrides are reported to exhibit higher catalytic activity
than single metal Mo carbides and nitrides. The role of support on the activity
of Mo carbides is yet to be investigated". Unsupported and supported Mo 2C
and Mo2N retained their crystallographic structure for long time ( 10 days)
during hydroprocessing reactions and hydrogen is contained in crystallites
surface and sub-surface region. Decrease in surface area and increase in
particle size cause considerable incre-ment in the catalyst activity per unit
surface. Information on carbides and nitrides of metals except molybdenum is
limited.
Catalyst stability is an important parameter governing the design of
catalyst. Mostly, catalyst activity decreases with time and it is due to the
localized blocking of active edges of catalysts. Additionally, coke formation
on catalyst surface leads to fouling. In general, catalyst acidity and its
deactivation rate are directly related.
Catalyst deactivation during hydrodeoxygenation can pose serious
problem on the reusability of the catalyst. Deactivation could be temporary or
permanent and permanent deactivation requires the replacement of catalyst. It
could be caused by catalytic poisoning or by loss of surface area (sintering).
Temporary deactivation is generally caused by deposition of carbon or sulfur
and the catalyst can be restored by gasification using air/stream mixtures.
Properly designed catalyst will represent minimum deactivation. All catalyst
undergoes deactivation (reversible/irreversible) at the hydrodeoxygenation
reac-tion conditions. However, the deactivation rate changes with catalyst. In
comparison to carbide and nitride catalysts, rate of catalyst deactiva-tion due
to coke formation is higher in the case of sulphided catalysts [121]. Using
H2S instead of CS2 as sulfur source in preparing sulphided catalysts shifted
the selectivity from C7 to C6 hydrocarbons. Leiva et al.
[135] investigated on the influence of water on the hydrodeoxygena-tion of
model compounds (2-methoxyphenol and phenol) using ReS 2/ SiO2 catalyst.
Influence of water on the hydrodeoxygenation activity of transition metallic
catalysts is still under debate. Some reports indicate the benign effects of
water while few literatures reports on the decrease in catalytic activity. Water
content is reported to reduce the dispersion of active metal and also inhibition
of intermediate reaction pathways. Additionally, degree of coke formation on
catalyst depends on temperature and pressure of reaction. Higher reaction
pressure can help in reduced coke formation. At any reaction temperature
between 350 1C and 375 1C, the degree of coke formation is minimum. At
lower temperatures, preference for hydrodeoxygenation reaction can be
subdued in comparison to other polymerization reactions if aromatic
compounds are used as feed stocks. Generally at higher temperatures, thermal
reactions which produce coke seems to occur and thus coke yield can
increase.
11. Conclusions
Overall, studies on hydrodeoxygenation of bio-based feedstocks to
produce green diesel (paraffins and olefins) is gaining attention in this decade.
Choice of feed stocks for the study should be based on the local availability of
the feedstock and its chemical properties such as degree of unsaturation and
the fatty acid content. Degree of unsatura-tion in a feed stock plays a vital role
in altering the reaction pathway and hence the product selectivity. Detailed
study on reaction pathway using model compounds such as fatty acids (oleic
acid, palmitic acid) or triolein is essential before using real feed stocks. From
this review, it is very evident that acidic support materials such as ZrO2, TiO2,
zeolites are preferred over basic and neutral support materials. Tailoring the
acidity of mesoporous support materials such as SBA-15, HMS, KlT-6 and
MCM-41 using aluminum, titanium or zirconium is essential as
253
these materials possess the desired physio-chemical properties but have low
acidity. Noble metals such as palladium, platinum and transition metals such
as nickel, molybdenum and cobalt are the most preferred active metals and
bimetallic systems generally show higher activity for hydrodeoxygenation.
Metals such as tungsten (W), vanadium (V) and iron (Fe) can work for
hydrodeoxygenation reaction as they have high affinity towards oxygen and
offer different oxidation states. Reports on the application of W, V and Fe for
HDO reactions are scarce. Active sites of a catalyst are related to morphology
and structure of catalyst and it is possible to establish a quantitative relation
between hydrotreating activity and number/type of active sites. Hence,
designing and controlling the exposed active sites can aid in altering the
catalyst reactivity. Reduction temperature of a catalyst can play a vital role in
the catalytic activity. Introduction of rare earth elements during catalyst
preparation can improve the thermal stability of the catalyst. In
hydrodeoxygenation reactions, promoters play a major role in increasing the
conversion rate and product selectivity. The most important factor to be
considered for the choice of promoter is promoter–support interaction.
Synthesized catalyst should have minimum promoter–support interaction to
ensure that the forma-tion of active sites are not hindered. For
hydrodeoxygenation reac-tions, it is recommended that metallic carbides and
nitride catalyst should be preferred over sulfide catalysts as the sulfur content
in the obtained products is of great environmental concern. Hydrodeox-
ygenation reaction is a process of great commercial significance and research
work should continue until the process is commercially viable worldwide.
Studies on engine tests using green diesel synthe-sized through HDO route,
emission studies and process economics can complement the research and
development activities related to the upgradation of bio-oils and bio-based
feedstocks.
Acknowledgments
Financial support from Natural Sciences and Engineering Research
Council of Canada (NSERC) is greatly acknowledged.
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