Escolar Documentos
Profissional Documentos
Cultura Documentos
Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-
Abstract:
Accepted Article
The catalytic decarboxylation of fatty acids to yield hydrocarbons, for a use as biofuel as a
main target, is a topical reaction in which the main challenge is actually to control the
selectivity while using the smallest amount of hydrogen possible (or even better, not using
hydrogen at all) in order to optimize cost-efficiency of the process. Herein, we draw a specific
point on the non-noble mono-, bi- and tri-metallic catalysts used to carry out this reaction.
different types of supports were first studied. Among such materials, the Co-based catalysts
were not selective, while, Cu-based catalysts were more or less selective to hydrocarbons or
to olefins, depending on the support used. Among these 3 metals, the Ni-based catalysts are
however the most described ones due to their specific ability to promote deoxygenation
reactions. Combining Ni to a second metal yielded a synergistic effect toward better catalytic
performances, with increases in both conversion and selectivity and also improvement of the
resistance of the catalyst to carbon deposit, especially when adding non-noble metals. For
future prospects, it appears that the main challenge will be to be able to maintain good
catalytic performances under inert gas further in solvent-free conditions, in order to yield a
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: 10.1002/jctb.5776
Deoxygenation (DO) reactions are widely used for producing the so-called “biofuels”
Accepted Article
from biomass-derived substrates, as an alternative to the currently massively used petroleum-
based fuels.1-5 DO consists of removing one or more oxygen atoms chemically bonded in the
organic molecules to be processed. Many studies dealing with DO of fatty acids (FAs) aiming at
producing linear hydrocarbons can be found in the literature.4-9 The most common DO reactions
consist on decarboxylation (DCX Eq. 1), decarbonylation (DCN, Eq. 2 and 3) and
hydrodeoxygenation (HDO, Eq. 4). In DCX and DCN, the whole functional group (carboxylic
acid moiety) is removed through carbon-carbon bond cleavage, releasing respectively CO2 or
CO, hence producing a hydrocarbon with one carbon atom less than that in the original fatty acid.
Both reactions can be carried out under inert atmosphere or optionally in the presence of a small
amount of hydrogen to improve the overall yield of the process.10-12 In contrast, HDO requires the
presence of a high quantity of hydrogen to reduce the oxygenated species present in the FA, but
leads to a hydrocarbon behaving the same number of carbon atoms as that in the original fatty
acid.13 While HDO is more atom economy efficient due to the preservation of the number of
carbons atoms of the molecular skeleton, HDX is more economically attractive because it needs
only very low amounts of hydrogen compared to the HDO reaction. Further, DCX and DCN
theoretically produce CO2 and CO, respectively, together with a carbon chain, which makes it
very interesting. For these reasons, DCX and DCN reactions have been extensively investigated
dehydrogenation can also occur depending on the reaction conditions. Furthermore, other
formed during DCX and DCN can lead to methanation (Eq. 5), (Eq.6) and water gas shift (Eq. 7)
reactions.14 Thus, a deep understanding of the factors governing the different routes and the side
Accepted Article
reactions is highly important to better control the selectivity and hence enabling optimization of
During the last decades, many studies on the DO of free fatty acids (FFA) and their derivatives
were conducted in order to elucidate the reaction mechanism.1, 8, 15, 16 First, it was demonstrated
that the DO pathway of fatty acids mainly depends on the nature of the catalyst used5 and on the
reaction atmosphere.17, 18 The behavior of the catalyst was found to be strongly related to the
Snåre and co-workers14 studied the DO of stearic acid (“SA”, C18 saturated fatty acid) under
6 bar of helium over a series of mono, bi and trimetallic catalysts supported on oxides,
Accepted Article
mesoporous materials or carbonaceous supports such as Al2O3, SiO2, Cr2O3, MgO, TiO2 and
active carbon (AC).14 The catalysts screening revealed that noble metals-based catalysts, namely
monometallic Pd and Pt supported on active carbon, exhibited the highest catalytic performances
at 300 °C. Pd/C was reported to act via a DCX reaction, while the use of Pt was found to favour
DCN. Pd was further found to be more active that Pt, and 5 wt.%Pd/C led to full conversion with
a selectivity to n-heptadecane as high as 95 %. Some studies were then carried out to optimize the
performances of Pd- and Pt-based catalytic systems.2, 24, 25, 26, 27, 28, 29 The influence of the nature
of the support was studied by Immer et al.18 They reported that supporting Pd over SiO2 favoured
DCN whereas Pd/Al2O3 and Pd/C solids exhibited a high DCX activity. Unfortunately, the
Pd/Al2O3 catalyst deactivated rapidly as compared to the Pd/C catalyst. In fact, supports
containing Brønsted acid sites also favoured isomerization reactions, and the presence of Lewis
acid sites further led to cracking and ketonization reactions.30, 31 The products issued from the
side reactions were largely responsible for the catalyst poisoning, which led to rather rapid
deactivation. In contrast, the high surface area of the carbon support (ca. 10 times larger than that
of alumina) enabled mitigation of the catalyst deactivation by coking or sintering due to the
presence of different functional groups on the carbon surface.14 Besides, the effect of the Pd
loading,32 of the amount of catalyst,2 the factors influencing deactivation of the catalyst such as
particle size growth and carbon deposit,33, 34 the substrate concentrations,24, 35 the solvent and the
reaction conditions such as temperature,36-40 the reaction pressure,32 the reaction time,32 the nature
of the atmosphere11 and the influence of the chain length of the saturated fatty acid20, 24, 32, 41 were
also respectively investigated. The liquid phase DCX reaction is preferentially carried out in a
and main products in the liquid phase, most frequently between 1 and 50 bar. At high temperature
(350 °C), the formation of undesired products resulting from cracking is observed, leading to a
Accepted Article
decrease in selectivity to the desired product.42 The nature of the gaseous atmosphere has also a
significant effect on the DO pathway, but the resulting effect strongly depends on the type of
metal used and on the FFA to catalyst ratio20 and then on the type of FFA (saturated and
unsaturated). For instance, the DO of stearic acid (saturated FFA) over Pd/C under inert
atmosphere or with a low hydrogen quantity (5 to 10 Vol. % H2 in N2) occurs via DCX, whereas
under higher concentration of hydrogen (100 Vol.% H2), DCN is dominant.18 It also appears that,
under low partial pressures of hydrogen (lower than 10 Vol.%), better conversion and selectivity
unsaturated fatty acids under inert gas leads to lower conversion to hydrocarbons and to an
increase in the deactivation of the catalyst due to the presence of highly unsaturated
compounds.13, 43, 44
In contrast, under hydrogen atmosphere, the deoxygenation pathway of
unsaturated fatty acids over Pd/C under H2 occurs firstly via the hydrogenation of the double
bonds to form a saturated fatty acid. This is due to the high hydrogenation activity of the Pd
catalysts.19 Then, through deoxygenation of the saturated acid, the final hydrocarbon is
Apart from the properties of the catalyst used and the reaction conditions, the fatty acids
chain length has also a rather strong impact on the DO catalytic performances in DO.20, 47 In fact,
the fatty acid conversion increases with the chain length, whereas the selectivity to hydrocarbon
decreases at the same time,32 due to the higher propensity of long-chain fatty acids to undergo
While noble metals-based catalysts have shown excellent results in the DO of fatty acids
Accepted Article
to n-alkanes,14 their fast deactivation is an issue impeding the economics of the derived process.10
Additionally, the high cost and low abundance of noble metals are subsequent serious concerns
catalysts showing good performances together with improved stability is of topical interest. That
is the reason why, in the last decade, developments of non-noble metal catalysts, which would be
highly active, selective and stable have been continuously growing. The literature concerning the
(noble and non-noble) has been already studied in details. The pathway followed for the FA
deoxygenation depends, on the one hand, on the catalyst properties (nature of the support, metal
particles size and dispersion, metal loading) and, on the other hand, on the conditions of reaction
(temperature, pressure, FFA/catalyst ratio, nature of the atmosphere, reaction time). For instance,
for the same Al2O3 support, Pd was reported to lead to an excellent selectivity to DCX products,
while Cu favored the DCN route. In the same way, Pd/C was very selective for DCX, while Pt/C
and Ni/C favored the DCN pathway. It is already well established that noble metals such as Pd
and Pt are effective in catalyzing the decarboxylation of fatty acids and their derivatives26-29. In
the same time, the deoxygenation of fatty acids was also studied over non-noble metal-based
catalysts such as Cu, Ni and Co. Among them, the Ni-supported catalysts showed the most
acid over Ni/C can reach 80% of conversion of SA at 81% of selectivity to heptadecane at
350 °C, under pure hydrogen. However, in their study, the optimization of the reaction over this
of stearic acid over Ni/C, but under inert gas to reduce the cost of the process. The results
obtained showed that the Ni/C catalysts led to complete conversion of SA and to 80% of
Accepted Article
heptadecane selectivity under inert gas at 370 °C.47 Unfortunately, to reach these catalytic
performances, the DCX reaction over Ni/C is performed at 70 °C above the temperature used for
Pd/C. Furthermore, the catalyst reached 80% of heptadecane selectivity compared to 99%
reached over 5 wt.%Pd/C.34-35 Although the Ni/C showed very promising results, this catalyst
still required improvements to reach a high selectivity to n-alkanes at a temperature much lower
than 370 °C. The influence of the nature of the metal on the DO of stearic acid to hydrocarbon
under hydrogen atmosphere was also studied.19 The catalysts based on Pd, Cu, Pt and Ni
supported on Al2O3 and WO3/ZrO2 were tested at 350 °C. The results showed that the activity of
the catalysts could be ranked as follows: Pd > Cu > Pt > Ni. The products distribution was also
very depending on the nature of the metal employed. 5 wt.% Pd/Al2O3 was reported to show an
selectivity to n-heptadecene.19 This is related to the fact that the activity for hydrogenation of a
catalyst based on copper is very low compared to that of a Pd-based catalyst, which will favor the
completely converted over 5 wt.% Pt/C within 2 h at 330 °C, and the selectivity to heptadecane
was 91%.19 The conversion efficiency of stearic acid over Ni/C was 7.4% per hour, while that of
stearic acid over Pt/C was 49.7% per hour. Although the conversion efficiency of Ni/C for
decarboxylation was not as good as Pt/C, the selectivities to heptadecane over Ni/C and Pt/C
were quite close, meaning that heptadecane can be selectively obtained over Ni/C using longer
reaction time or higher temperature.19 However, it would be very difficult to compare activity of
both catalytic systems (noble and non-noble catalysts). Catalysts tests should be performed under
As aforementioned, both the metal and the support play a crucial role in the DCX reaction.48
Obviously, their nature and combination strongly impacts the performances of the as-designed
catalytic systems, among other parameters less sensitive. Such factors influencing the catalytic
activity of the monometallic supported catalysts are discussed below in regard to the literature.
monometallic (Ni, Co and Cu) catalysts supported on ZrO2 for the catalytic DCX of SA to
heptadecane at 330 °C under inert atmosphere (Table 1 entries 1, 2 and 3). The Co based catalyst
was more active (75 % of conversion), but not at all selective to the DCX reaction, with a very
low selectivity to heptadecane (9 %). Unfortunately, the main product formed was not identified
in this paper. In contrast, the nickel catalyst exhibited a fairly average conversion (37 %) but with
a relatively high selectivity to heptadecane (79 %). The results over the Cu-based catalyst were
less convincing than over Ni/ZrO2, with 36 % conversion and a rather modest selectivity to SA of
23 %.
Hence, among the non-noble monometallic catalysts studied for the DCX of fatty acids,
Ni is the most interesting metal, as it is actually simultaneously active and selective. In addition,
Ni-based materials are cheap as compared to other metal-based catalysts, explaining the fact that
It is well known that the catalytic performances of the supported species can be tuned
depending on the properties of the support used,20, 54-56 which is obviously the case of metal-
Accepted Article
based catalysts.57 Various supports such as SiO2, Ce2O3, Al2O3, CrO3, and TiO2, C, basic
composite oxides, bifunctional acid-base oxides (ZrO2), and zeolites were studied on DCX
reactions.
carbon and silica. The results, obtained at 300 °C for 5 h, under inert atmosphere, showed that Cu
was more active (36 % conversion) and less selective to n-heptadecane (23 %) when it was
supported on zirconia (Table 1, entry 1) than when the support was alumina, with 17 %
conversion and an n-heptadecane selectivity of 59 % (Table 1, entry 4). Similarly, Ni/C showed
37 % of conversion and 89 % of selectivity (Table 1, entry 5), whilst over Ni/ZrO2 the conversion
was the same (37 %) with a lower selectivity (79 %) (Table 1, entry 3). Concerning the catalytic
performances of the 40 wt.%Ni/SiO2 catalyst, the conversion and the selectivity to n-heptadecane
were 54 % and 51 % respectively, with a yield of n-heptadecane lower than that obtained using
20 wt.%Ni/C (28 % vs. 33 %). Among the catalysts tested by Wu et al., Ni/C was the most
Snåre et al.14 have compared the results of the catalytic DO of stearic acid over nickel-
based catalysts with different nickel contents over Al2O3, SiO2 and CrO3, benchmarked against
the results over Raney Ni. The reactions were carried out at 300 °C under 6 bar of helium for 6 h.
Table 2 shows that, under such conditions, all the nickel-based catalysts performed quite poorly,
with a conversion less than 20 %. Further, these catalysts are prone to cracking and to the
formation of heavier products such as dimers,58, 59 while not favouring the HDO route (selectivity
which was also the catalyst showing the lowest selectivity to 1-heptadecene. The Ni/SiO2 catalyst
showed the highest selectivity toward 1-heptadecene. In all cases, the nickel-based catalyst
Accepted Article
favored the formation of several side reactions.14 Snåre et al.14 found also that 1-heptadecene was
the dominant product in the liquid phase during the DO of stearic acid over Ni/SiO2 catalyst. In
contrast, these results are the opposite to the results of Wu et al.47 who found that for the same
catalyst, n-heptadecane was the main product. The difference of the results observed could be
attributed to the difference of the reaction conditions. Unfortunately, the other catalysts studied
by both authors were not the same and consequently, it is impossible to draw deeper comparative
conclusions.
Crocker and co-workers reported the performances of Ni-Al LDH (Ni-Al layered double
hydroxide catalyst), 20 wt.%Ni/Al2O3 and 20 wt.%Ni/C catalysts in the DCX and DCN reactions
of stearic acid at 300 °C for 1.5 h (Table 3) as a function of the atmosphere composition (N2,
10 Vol.% H2 in N2 or H2).56 The 20 wt.%Ni/Al2O3 and Ni-Al LDH catalysts gave 81 and 73 % of
respectively, when the reaction was carried out in the presence of pure hydrogen, which was
much higher than the performances observed under N2 with respective values of 9 and 10 % in
consisting of 10 %H2 in N2, the 20 wt.%Ni/Al2O3 catalyst showed almost a constant conversion
(80 %) and a slight increase in n-heptadecane selectivity (67 %). The authors suggest that the
difference of the results underlines the fact that there are interactions between hydrogen content
and Ni-specific surface area.60 However, regarding the 20 wt.%Ni/C, the catalytic performances
(80 % of conversion and 81% of selectivity) were slightly higher than that observed over
conversion and 52 % of selectivity) catalysts under the hydrogen atmosphere. To understand the
impact of the atmosphere on the DO reaction, the authors studied the kinetics of the reaction at 0,
Accepted Article
0.5, 1 and 1.5 h duration performed over 20 wt.%Ni/C under pure H2. The observation made
showed that the hydrogen concentration in the gas feed has an influence on the rate of the
formation of the products and then, on the selectivity to the desired product. Indeed, the DO rate
In all cases, irrespective of the reaction atmosphere and the catalyst used, selectivities to
the products formed by cracking reactions are higher than that of the desired n-heptadecane
product (Table 3). These results confirm those obtained by Snåre et al.14 who showed that the
Among the studied nickel-based solids, the carbon-supported ones enabled reaching
higher selectivity to n-heptadecane under inert atmosphere. In fact, it was reported that the carbon
support does not promote DO.9 Then, there is no need to add hydrogen in the reactant atmosphere
to maintain their activity. In contrast, the reducible oxide supports such as TiO2, ZrO2, Al2O3,
CrO3, etc., need to work under hydrogen-containing conditions to prevent the coke deposition
and maintain their activity.9 Thus, besides the support, the composition of the gas atmosphere is a
Al2O3 and WO3/ZrO2 in the DO of stearic acid to hydrocarbons under 14 bar of hydrogen at
350 °C after 6 h of reaction. The results (Table 4) showed that, when Ni and Cu were supported
on Al2O3, the conversions were 60 and 95 %, respectively, and that the selectivities to total C17-
hydrocarbons were 60% and 81%, respectively. Therefore, this suggests that Cu favors the DCN
Ni, direct or indirect DCX was favored. In contrast, when Ni and Cu were supported on a
WO3/ZrO2 mixed oxide, the conversions reached the highest values (100% and 99 %
Accepted Article
respectively), but the selectivities to DCX/DCN product decreased significantly (only 11% and
on alumina. Thus, alumina seems to favor DCX and DCN reactions, while the use of WO3/ZrO2
as a support enhances side reactions such as cracking. More precisely, the authors suggest that the
WO3/ZrO2 mixed oxides favor the cracking reaction of the unsaturated chains formed during the
DCN reaction due to their acidity. These assumptions were based on the high quantity of CO
detected in the gas phase (~80 % of CO selectivity). These results confirm that, Ni/Al2O3 is a
potential catalyst for DCX of stearic acid to hydrocarbon. However, this catalyst requires the
presence of hydrogen in the atmosphere to improve its catalytic performances14, 60 and to maintain
its activity. That is why the use of a hydrogen-containing atmosphere was necessary to
hydrogenate the unsaturated chain (1-heptadecene) formed via DCN and avoiding the rapid
deactivation of the catalyst. Indeed, the presence of unsaturated hydrocarbons increased the coke
Peng et al.62 also studied the impact of the support on the DO of SA to n-heptadecane.
10 wt.% of Ni were supported on ZrO2, TiO2, Al2O3, CeO2 and SiO2. The catalytic reactions were
performed at 260 °C under 40 bar of H2 in the batch mode, and the results are given after 8 h of
reaction (Table 5). Complete conversions of SA over Ni/ZrO2 and Ni/CeO2 were observed with
were observed over Ni/Al2O3 and Ni/SiO2 with 63 and 45 %, respectively, while selectivities to
n-C17 were 81 and 57 %, respectively. However, these latter catalysts also showed 14 % and
to 1-octadecanol were lower, with values of 1.2, 6.7 and 3.5 %, respectively. Furthermore, in all
cases, the selectivity to n-C18 (namely the product of the HDO route) was lower than 2 %, except
Accepted Article
over Ni/TiO2 with a 5 % selectivity to n-C18. Therefore, among the four catalysts studied, the
Similarly, Peng et al.30 also investigated the impact of the support on the DO of PA
(palmitic acid) over nickel supported on ZrO2, Al2O3, SiO2 and zeolites HBEA (Si/Al:180) and
HZSM-5 (Si/Al:200). The reaction was performed at 260 °C, under 12 bar of H2 for 6 h. The
results (Table 6) showed full conversion over the Ni/ZrO2, Ni/HBEA and Ni/HZSM-5 catalysts.
The selectivities to n-pentadecane were lower over zeolites with 24 % and 21 % over Ni/HBEA
and Ni/HZSM-5, respectively, while the selectivities to n-C16 products susceptible to be formed
from HDO were larger on these latter catalysts with values of 49 and 59 %, respectively.
Furthermore, when supported on zeolites, Ni led also to the formation of iso-alkanes and iso-
alkenes, while the latter were not found when Ni was supported on other supports. The lowest
conversions were obtained over Ni/Al2O3 and Ni/SiO2 with 51 and 41 %, respectively, while the
selectivities to n-pentadecane were 74 and 59 %, respectively. Among all the studied catalysts,
the Ni/ZrO2 sample was the most active in terms of conversion and selectivity.
The reaction mechanism for the deoxygenation of fatty acid to n-alkanes via synergetic
catalysis over Ni/ZrO2 in the presence of H2 is showed in Figure 1. First, the carboxylic group of
fatty acid adsorbs on the oxygen vacancies of ZrO2 to form carboxylates species.30 Then, H2
undergoes dissociative adsorption at oxygen defect sites. The abstraction of the α-hydrogen atom
produces an aldehyde intermediate and H2O. This aldehyde intermediate is then subjected to
DCN on metallic Ni to give a hydrocarbon. The presence of hydrogen allows the oxide support to
Figure 1 : Reaction mechanism for the deoxygenation of fatty acid to n-alkanes via synergetic catalysis over Ni/ZrO2 in the
However, in the presence of Ni/ZrO2, under inert atmosphere, the conversion decreased
from 100 to 3.5 % and the DCX did not occur (no formation of n-alkane). The product formed
Na et al.64 studied the DCX of oleic acid in the absence of hydrogen using only basic
supports (MgO-Al2O3) without any metal phase. It was reported that most of the oxygen atoms in
oleic acid were removed under the form of CO2 and n-heptadecane was obtained. However, very
low selectivity was obtained due to cracking reactions, which occurred simultaneously.
In contrast, Roh et al.65 investigated the DCX of oleic acid over Ni supported on basic
composite oxides supports (Ni/MgO-Al2O3). The effect of preparation mode of the catalyst
including the catalyst calcination temperature (300, 400 or 500 °C) and the reaction conditions
such as the temperature (300, 350 and 400 °C), the pressure and the reaction time were examined.
The authors reported that, over the Ni/MgO-Al2O3 catalyst, the reaction occurred mainly through
temperature range from 300 to 350 °C. Indeed, the conversion of oleic acid varied from 31.3 % to
67.5 % with the corresponding selectivity to n-heptadecane ranging from 4.8 % to 12.5 %. The
Accepted Article
authors reported that the good performances obtained on the catalyst calcined at 300 °C were
mainly due to the presence of free Ni species on the surface, which have a beneficial effect on the
Figure 2: Reaction routes for the DO of oleic acid to alkanes over Ni/ZnO-Al2O3. Adapted from Ref.66
Li et al.66 studied the DO of oleic acid over Ni supported on basic supports, namely on
basic composite oxides (MO-Al2O3, with M = Mg, Ca, Ni, Cu or Zn) at 280 °C. The metal
loading was 10 wt.% for each catalyst. The distribution in the liquid products depended on the
nature of the support and also on their preparation method (Table 7). The distributions of the
products observed for catalysts prepared by a procedure similar to that used for the preparation of
and for the catalyst purchased from Sasol Company (denoted as Ni/ɣAl2O3-2) were not the same
acid. Among all the tested catalysts, the Ni/ZnO-Al2O3 sample showed the highest selectivity to
n-heptadecane. The authors also studied the effect of the different reaction conditions such as
Accepted Article
temperature, H2 pressure and reaction time on the catalytic performances of the Ni/ZnO-Al2O3
catalyst. They found the best results at 300 °C, at 2 MPa for 6 h of the reaction (total conversion
of oleic acid and 96.2 % of selectivity to n-heptadecane). They followed the kinetic of the
reaction during 6 h and they observed the formation of the distribution of the products as a
function of the reaction time. The results suggested that n-heptadecane was mainly derived from
stearyl stearate hydrogenolysis to octadecanal with subsequent octadecanal DCN, which was the
main route in the whole reaction pathway (Figure 2). In fact, during the first hours of reaction, the
hydrogenation of the double bond C=C in oleic acid occurred and stearic acid was formed. The
authors suggest that one part of stearic acid was converted to n‐heptadecane by direct
decarboxylation, and a small amount of stearic acid was hydrogenated to 1‐octadecanol. Then,
stearyl stearate was also formed from 1‐octadecanol reacted with the stearic acid. Intermediate
The differences in the results observed in the literature for the catalysts based on different
supports are due to the physical and chemical properties of the supports. Indeed, the nature of the
acid sites of the supports influences the catalytic activity and selectivity. The abundance of
Brønsted acid sites favored the HDO routes, while the Lewis acid sites present for example in the
ZrO2, Al2O3, or SiO2 supports tend to favor the reaction hydrogenation of FFA followed by a
decarbonylation. In some cases, the results showed that the deoxygenation of SA over carbon-
based catalyst proceeds via decarboxylation, whereas the SiO2 support favored decarbonylation.
startes at lower temperatures than activated carbon. Unfortunately, this catalyst deactivates,
rapidly. The better stability of the active carbon as support was attributed to the high surface area
Accepted Article
of the carbon support and to its amphoteric properties able to reduce the formation of coke
inducing catalyst deactivation.14 In the same way, the acid-base properties of the supports will
influence the catalytic activity. High basicity of the support will favor the DO reaction of acids to
alkanes.67
Unfortunately, the influence of the nature of the support on the reduction of metals is not
discussed in the literature in the decarboxylation reaction even if the presence of metal under a
reduced state is crucial to obtain high activity. The reduction of supported Ni2+ ions depends on
the acidity of the support. Over poorly acidic supports such as crystallized silica or ceria, the
reduction of nickel is facilitated. In contrast, over highly acidic supports such as amorphous
silica, alumina, and niobia reduction of nickel will be more difficult. Indeed, the presence of
strong metal-support interaction will play a leading role in the reduction process and will
influence the extent of reduced metal. Support will also influence the average particle size of
metallic nanoparticles.
1.3.Effect of Ni loading
The metal loading is with any doubt one of the most important factors in the decarboxylation
reaction. The loading governs the dispersion (particle size) of the metallic nanoparticles.
Unfortunately, even if several research groups studied the effect of metal loading only few
articles discuss on the factors influencing the overall catalytic activity (dispersion, particle size,
structure, morphology).
studied by a few research groups. Among them, Peng et al.30, 62 explored the effect of the metal
loading on the DO of SA and PA. The reaction was carried out at 4 different Ni loadings, namely
Accepted Article
3, 5, 10 and 15 wt.% supported on ZrO2. For the DO of SA, the results revealed that the highest
conversion (100 %) and selectivity to n-heptadecane (96 %) were reached for 10 and 15 wt. % of
Ni as shown in Table 5. Similarly, for the DO of PA, the results obtained (Table 6) showed that
the conversion of PA was full, except for the catalyst loaded at 3 wt.% (67 % of conversion only).
The highest selectivity was obtained for the 5 wt.% Ni/ZrO2 catalyst (Table 6). Unfortunately,
these authors did not discuss the effect on nickel particle size on the catalytic activity. It was
observed that the SA conversion was full for all the nickel loadings. However, differences in
specific reaction rates could be obtained. The rate strongly depended on the average Ni particle
size. The highest rate was obtained for the 15 wt.% Ni/ZrO2 catalyst, which presented also the
biggest mean particles’ size (18 nm). This indicates that the adsorption of SA on nickel surface
While the Ni loading on ZrO2 was the same in both studies (in the DCX of SA and PA,
respectively) the catalytic activity was very different. Indeed, 10 wt.%Ni/ZrO2 showed the best
catalytic activity in the DCX of stearic acid, whereas in case of PA conversion, 5 wt.%Ni/ZrO2
was the best sample. Thus, the catalytic DCX of FFA depends not only on the metal loading but
also obviously on the catalyst properties, on the FFA chain length and on the reaction conditions.
Wu et al.47 studied also the DO of SA over 3 different metals loadings namely 10, 20 and
30 wt.%. The reaction was performed under inert atmosphere at 330 °C for 5 h. The catalyst
loading was 30 mg and the stearic acid loading was 0.176 mmol. The results showed that the
conversion increased with the nickel loading (Figure 3). The selectivity to n-heptadecane was
Figure 3. Effect of the Ni loading on the catalytic DCX reaction of stearic acid (SA). Reaction Conditions:
T = 330 °C, time = 5 h, catalyst loading = 30 mg, stearic acid loading = 0.176 mmol. In blue, conversion of stearic
Unfortunately, the authors did not explain this observation. They stated only that bigger
nickel particles could block pore of the carbon support decreasing the total pore volume.
However, the difference in pore volume between 20 and 30 wt.% of Ni (0.57 vs. 0.55 cm3g-1,
respectively) are negligible as compared to the high difference in conversion (39 and 61 %
respectively) and selectivity (90 and 72 %, respectively). The effect of pore blockage is not the
only factor responsible for the differences observed in terms of catalytic activity.
20 wt.%Ni/C catalyst working under the same operating conditions. The reactions were
performed at 350 °C under inert atmosphere for 3 h. The highest activity and selectivity were
Accepted Article
obtained for the DCX of the FAs with the shorter chain length (C12 to C14) (Figure 4).
In general, it was reported that the fatty acid conversion decreased when the carbon length
chain increased. Similarly, the selectivity to the corresponding n-hydrocarbon decreased when the
carbon chain length increased. Such a decrease in selectivity was attributed to the higher
propension of long-chain fatty acids undergo cracking. Thus, over the 20 wt.%Ni/C catalyst,
conversion of a shorter fatty acid chain rather occurred through DCX while with longer FAs
cracking reactions were favored. The authors concluded that, for different fatty acids having
similar chain lengths, the catalytic performances should be quite similar over the same catalyst
Figure 4. Catalytic performances of a carbon-supported nickel catalyst (20 wt.% Ni/C) in the DCX of different
saturated fatty acids. Reaction Conditions: T = 350 °C, time = 4 h, catalyst loading = 30 mg, fatty acid
loading = 0.20 mmol. (a) correspond to the conversion of each fatty acid. (b) corresponds to the selectivity and yield
to the corresponding hydrocarbons with one carbon atom less than the original fatty acid, i.e., LA: lauric acid to
undecane (C11); myristic acid to tridecane (C13); Palmitic acid to pentadecane (C15); stearic acid to heptadecane
(C17); arachidic acid to nonadecane (C19), and behenic acid to heneicosane (C21). Results adapted from Ref.47
Hermida et al.68 studied the solvent-free palmitic acid DO over nickel metal incorporated
into mesostructured cellular foams (NiMCF). The reaction was carried out in a semi-batch reactor
at 300 °C with a Ni loading of 15 wt%.68 The main products were n-pentadecane and n-
more or less, higher than that of n-pentadecene. In fact, the authors reported that the DCX
reaction times longer than 3 h. Besides the DCX and DCN reactions, the C18 product derived
from HDO was also observed. In addition, other reactions such as ketonization and cyclisation
Accepted Article
also occurred, but not significantly. However, the selectivities were not mentioned in this work.
The authors also studied the recyclability of the catalyst. Unfortunately, the NiMCF catalyst was
not stable and its deactivation was fast. The authors reported that this deactivation was due to the
phase transformation of the metallic nickel (Ni0) into the nickel ion (Ni2+) and the deposition of
the organic molecules on the surface catalyst during the reaction (coking).
studied the catalytic DO of stearic acid over alumina-supported bimetallic Ni-Cu and Ni-Sn
catalysts. The reactions were performed at two different temperatures (260 and 300 °C), under
20 bar of H2 and for 1.5 h. The results are shown in Table 8. Cu, contrary to Sn, is a very
effective promoter of Ni for the DCX/DCN reaction of stearic acid at both temperatures. SA
Cu/Al2O3 at 300 °C, together with an increase in selectivity to C17 from 66 to 79 %. The reasons
of this promoting effect of Cu is that Cu enhances the reducibility of Ni and suppresses both
cracking reactions and coke-induced deactivation.63 In fact, it was mentioned that the Cu
occupied edges sites, which are preferentially the sites of the formation of carbon deposits on Ni
particles.69
study the performances of a trimetallic NiSnK/SiO2 catalyst in the DO of palmitic acid at three
different temperatures (250, 300 and 350 °C). First, as expected, the highest conversion (about
Accepted Article
90 %) of palmitic acid was achieved at 350 °C. Second, they studied the effect of the WHSV
(weight hourly space velocity) on the palmitic acid conversion. They found that the conversion of
PA decreased with an increase in the space velocity. Finally, they studied also the influence of
the time of reaction, varying the WHSV and they found that when the contact time increased,
some DCN and isomerization products. Unfortunately, the selectivities to C15 were not reported
in this paper.42
4. Reaction pathway
depends on the atmosphere of the reaction. Actually, it was observed that some routes are more
dominant than others depending on reaction conditions and the type of catalyst used. Based on
the results obtained on different catalysts, the reaction pathway represented on Figure 5 can be
proposed under three different atmospheres (inert, rich and low-hydrogen content). Under H2-
containing atmosphere, the DCN of fatty acids occurs via an intermediate aldehyde formation and
a subsequent ketene intermediate formation,whereas DCX occurs via a direct route or via a
decomposition, by releasing formic acid and subsequent hydrogenation of the formed olefin.13
The DO pathway of unsaturated fatty acids under H2 occurs firstly via the hydrogenation of the
double bonds to form a saturated fatty acid Then, through DO of the as-formed saturated acid, the
Figure 5: Proposed reaction route for the DO of fatty acid to n-alkanes. Adapted from the results of 7, 14, 66
Under inert atmosphere, Murzin et al.14 determined the reaction routes in stearic acid DO
over several heterogeneous catalysts at 300 °C. Apart from the DCX and DCN reactions,
produced shorter fatty acids and hydrocarbons, whereas ketonization produced symmetrical
ketones. n-alkane and n-olefins isomers were also formed. Finally, cyclic and aromatic products
were also produced, but in very low amounts.13, 14 Under inert atmosphere, the DO of unsaturated
fatty acid occurred firstly via the hydrogenation of the double bonds (C=C) to form the
Generally, the hydrogen needed to carry out this step originates either from residual H2 present
on the catalyst surface, which is adsorbed during the reductive pretreatment,2, 13 or from in situ
Accepted Article
formation via the simultaneous dehydrogenation reactions of the feed to unsaturated by-products
DO of saturated fatty acid, the DO of unsaturated fatty acid under inert gas leads to low
conversion to hydrocarbons and to an increase in the deactivation extent due to the presence of
Concerning the operating conditions, the bibliographic study has shown that the liquid phase
DCX reaction is preferentially carried out in a temperature range from 250 to 380 °C. The applied
pressure (between 1 and 50 bar) is chosen in order to maintain the reactants and main products in
the liquid phase. An increase in pressure was found to slightly decrease the conversion and
increase the selectivity, keeping the yield of alkane constant. In contrast, an increase in reaction
temperature was found to increase in a certain extent both conversion and selectivity. However,
at too high temperature (350 °C) the formation of undesired products resulting from cracking
occurs, and this leads to a decrease in selectivity to the desired products. Similarly, an increase in
reaction time enhances the cracking and other consecutive reactions leading to a significant
decrease in selectivity to the desired product by the formation of isomers and/or oligomers.
Therefore, the reaction should be preferably carried out at short reaction times (1 to 6 h for
example). The gas atmosphere was also found to have a significant effect on the DO pathway, but
this effect strongly depends on the type of metal used and on the FFA/catalyst ratio. For instance,
occurred via DCX, whereas under higher concentration of hydrogen DCN is dominant. It also
appears that under low partial pressures of hydrogen (10 Vol.%) better conversion and selectivity
Accepted Article
to alkane can be obtained. Apart from the properties of the catalyst used and the reaction
conditions, the fatty acids chain length also has an impact on the catalytic performances in DO. In
fact, the conversion of the fatty acids increases with the acid chain length, whereas the selectivity
to hydrocarbon decreases, due to the ease of long-chain fatty acids to crack. Therefore, for fatty
acid having similar chain lengths, the difference in catalytic performances should not be
significant.
Finally, based on the literature, the main challenges in the field of fatty acids
decarboxylation could be drawn. One of the most challenging parts consists on the catalyst
recyclability and stability. If the catalyst deactivates completely after a certain number of
consecutive tests, it would be important to find a method to regenerate it using for example
hydrogen treatment. Indeed, hydrogen is known to enable regeneration of the catalysts via coke
continuous reactors and the design of a continuous process would be very interesting from an
industrial point of view. In order to extend the application of non-noble based catalysts to other
substrates, it might be also advantageous to test the activity of these catalysts, using unsaturated
fatty acids and also on PFAD (Palm Fatty Acid Distillate). Indeed, the PFAD is a residue from
palm oil refining process consisting of over 85% of FFA. However, the application of known
catalysts for the decarboxylation of PFAD, is very difficult due to the impurities present in this
mixture. The development of new metallic or bi-metallic catalysts resistant to the impurities
This review summarizes the recent studies of non-noble metal-based catalysts in the
decarboxylation of fatty acids to hydrocarbons. Four main factors, namely the nature of the
Accepted Article
catalyst, the nature of the fatty acid, i.e., its chain length and its saturation or unsaturation, the gas
atmosphere, and the reaction conditions are the main parameters that influence the deoxygenation
pathways. The nature of the heterogeneous catalyst depends itself on three mains parameters: the
active phase, the support and the preparation method.21, 70-72 The nature of the metal plays a
crucial role on the reaction mechanism. Among the studied catalysts, the Ni-based catalysts
showed very promising results and are worth to be studied in the decarboxylation reactions.
However, many researchers suggest that the Ni-based catalysts also favor the C–C cleavage,73
and the deposition of carbon,74 which is responsible for the rapid deactivation of the catalysts.
Combining Ni to a second metal such as Cu was found to enhance not only the performances of
the catalyst but also to improve carbon resistance.67, 75 Besides, combining Ni with two other
metals (Sn, K), also yielded improvement of the catalytic performances. Moreover, the support
played an important role in the reactivity of the catalyst impacting the primary reactions and then,
the final selectivity of the reaction.76 Furthermore, depending on the properties of the support, the
catalyst requires the use of inert, poor- or rich-hydrogen atmosphere. For instance, with catalysts
supported on oxides, the presence of rich hydrogen atmosphere seems to be mandatory, while in
the case of inert supports such as activated carbon, the use of hydrogen-rich atmospheres is not
necessary, which enables designing a cheaper process. Another way to reduce the cost of the
process and also to provide an environmentally friendly solution is to perform the reaction under
solvent-free conditions.77-79
This work was supported by Weylchem. The authors would like to thank Dr. Olivier Simon and
Hauts-de-France and FEDER are acknowledged for supporting and funding partially this work.
References
1. Hermida L, Abdullah AZ and Mohamed AR. Deoxygenation of fatty acid to produce diesel-like
hydrocarbons: A review of process conditions, reaction kinetics and mechanism. Renew. Sus. Energy Rev.
2. Mäki-Arvela P, Kubickova I, Snåre M, Eränen K and Murzin DY. Catalytic Deoxygenation of Fatty Acids
3. Stepacheva АA, Sapunov VN, Sulman EMSM, Nikoshvili LZ, Sulman MG, Sidorov AI, Demidenko GN and
Matveeva VGG. Catalytic Hydrodeoxygenation of Fatty Acids for Biodiesel Production. Bull. Chem. Reac.
4. Li D, Xin H, Du X, Hao X, Liu Q and Hu C. Recent advances for the production of hydrocarbon biofuel via
5. Veriansyah B, Han JY, Kim SK, Hong S-A, Kim YJ, Lim JS, Shu Y-W, Oh S-G and Kim J. Production of
renewable diesel by hydroprocessing of soybean oil: Effect of catalysts. Fuel. 94(Supplement C):578-85
(2012).
6. Pattanaik BP and Misra RD. Effect of reaction pathway and operating parameters on the
deoxygenation of vegetable oils to produce diesel range hydrocarbon fuels: A review. Renew. Sus. Energy
9. Gosselink RW, Stellwagen D and Bitter, JH. Tungsten‐Based Catalysts for Selective Deoxygenation.
10. Santillan-Jimenez E and Crocker M. Catalytic deoxygenation of fatty acids and their derivatives to
triglycerides and fatty acids to hydrocarbons over carbon-supported nickel. Fuel. 103:1010-7 (2013).
12. Kubičková I, Snåre M, Eränen K, Mäki- P and Murzin DY. Hydrocarbons for diesel fuel via
13. Gosselink RW, Hollak SA, Chang SW, van Haveren J, de Jong KP, Bitter JH and van Es DS. Reaction
pathways for the deoxygenation of vegetable oils and related model compounds. ChemSusChem.
6(9):1576-94 (2013).
14. Snåre M, Kubičková I, Mäki-Arvela P, Eränen K and Murzin DY. Heterogeneous Catalytic
Deoxygenation of Stearic Acid for Production of Biodiesel. Ind. Eng. Chem. Res. 45(16):5708-15 (2006).
15. Dragu A, Kinayyigit S, García-Suárez EJ, Florea M, Stepan E, Velea S, Tanase L, Collière V, Philippot K,
Granger P and Parvulescu VI. Deoxygenation of oleic acid: Influence of the synthesis route of
Pd/mesoporous carbon nanocatalysts onto their activity and selectivity. Appl. Catal. A: Gen.
16. Anthonykutty JM, Linnekoski J, Harlin A and Lehtonen J. Hydrotreating reactions of tall oils over
24(10):5291-9 (2010).
18. Rozmysłowicz B, Mäki-Arvela P, Tokarev A, Leino A-R, Eränen K and Murzin DY. Influence of Hydrogen
Accepted Article
in Catalytic Deoxygenation of Fatty Acids and Their Derivatives over Pd/C. Ind. & Eng. Chem. Res.
51(26):8922-7 (2012).
19. Berenblyum AS, Shamsiev RS, Podoplelova TA and Danyushevsky VY. The influence of metal and
carrier natures on the effectiveness of catalysts of the deoxygenation of fatty acids into hydrocarbons.
20. Ford JP, Immer JG and Lamb HH. Palladium Catalysts for Fatty Acid Deoxygenation: Influence of the
Support and Fatty Acid Chain Length on Decarboxylation Kinetics. Top. in Catal. 55(3):175-84 (2012).
21. Schwarz JA, Contescu C, Contescu A. Methods for Preparation of Catalytic Materials. Chem. Rev.
95(3):477-510 (1995).
22. Gil A, Díaz A, Gandía LM and Montes M. Influence of the preparation method and the nature of the
support on the stability of nickel catalysts. Appl. Catal. A: Gen. 109(2):167-79 (1994).
23. van Haasterecht T, Swart M, de Jong KP and Bitter JH. Effect of initial nickel particle size on stability of
nickel catalysts for aqueous phase reforming. J. Energy Chem. 25(2):289-96 (2016).
24. Simakova I, Simakova O, Mäki-Arvela P and Murzin DY. Decarboxylation of fatty acids over Pd
25. Kilpiö T, Mäki-Arvela P, Salmi T and Murzin DY. Modeling of the catalytic deoxygenation of fatty acids
in a packed bed reactor. Multiphase Catalytic Reactors: John Wiley & Sons, Inc.; 2016. p. 365-76.
26. Yang L and Carreon MA. Deoxygenation of Palmitic and Lauric Acids over Pt/ZIF-67
Membrane/Zeolite 5A Bead Catalysts. ACS Appl. Mater. Interfaces, 9 (37): 31993–32000 (2017)
27. Yang L and Carreon MA. Effect of reaction parameters on the decarboxylation of oleic acid over
Pt/ZIF‐67 membrane/zeolite 5A bead catalysts. J. Chem. Technol. Biotechnol. 92(1): 52-58 (2017)
29. Ahmadi M, Macais E, Jasinksi J, Ratnasamy P amd Carreon M. Decarboxylation and further
Accepted Article
transformation of oleic acid over bifunctional, Pt/SAPO-11 catalyst and Pt/chloride Al2O3 catalysts. J. Mol.
30. Peng B, Zhao C, Kasakov S, Foraita S and Lercher JA. Manipulating Catalytic Pathways: Deoxygenation
31. Liu Y, Yao L, Xin H, Wang G, Li D and Hu C. The production of diesel-like hydrocarbons from palmitic
acid over HZSM-22 supported nickel phosphide catalysts. Appl. Catal. B: Envi. 174(Supplement C):504-14
(2015).
32. Mohite S, Armbruster U, Richter M, Martin A. Impact of Chain Length of Saturated Fatty Acids during
33. Ping EW, Pierson J, Wallace R, Miller JT, Fuller TF and Jones CW. On the nature of the deactivation of
supported palladium nanoparticle catalysts in the decarboxylation of fatty acids. Appl. Catal. A: Gen.
396(1–2):85-90 (2011).
34. Madsen AT, Rozmysłowicz B, Simakova IL, Kilpiö T, Leino A-R, Kordás K, Eränen K, Mäki-Arvela P and
Murzin DY. Step Changes and Deactivation Behavior in the Continuous Decarboxylation of Stearic Acid.
35. Mäki-Arvela P, Rozmysłowicz B, Lestari S, Simakova O, Eränen K, Salmi T and Murzin DY. Catalytic
Deoxygenation of Tall Oil Fatty Acid over Palladium Supported on Mesoporous Carbon. Energy & Fuels.
25(7):2815-25 (2011).
36. Bernas H, Eränen K, Simakova I, Leino A-R, Kordás K, Myllyoja J, Mäki-Arvela P, Salmi T and Murzin
DY. Deoxygenation of dodecanoic acid under inert atmosphere. Fuel. 89(8):2033-9 (2010).
38. Rozmysłowicz B, Mäki-Arvela P, Lestari S, Simakova OA, Eränen K, Simakova IL, Murzin DY and Salmi
Accepted Article
TO. Catalytic Deoxygenation of Tall Oil Fatty Acids Over a Palladium-Mesoporous Carbon Catalyst: A New
39. Lestari S, Simakova I, Tokarev A, Mäki-Arvela P, Eränen K and Murzin DY. Synthesis of Biodiesel via
Deoxygenation of Stearic Acid over Supported Pd/C Catalyst. Catal. Lett. 122(3):247-51 (2008).
40. Simakova I, Simakova O, Mäki-Arvela P, Simakov A, Estrada M and Murzin DY. Deoxygenation of
palmitic and stearic acid over supported Pd catalysts: Effect of metal dispersion. Appl. Catal. A: Gen.
355(1–2):100-8 (2009).
41. Lestari S, Mäki-Arvela P, Simakova I, Beltramini J, Lu GQM and Murzin DY. Catalytic Deoxygenation of
Stearic Acid and Palmitic Acid in Semibatch Mode. Catal. Lett. 130(1):48-51 (2009).
42.Chiam LT and Tye. CT. Deoxygenation of plant fatty acid using NiSnK/SiO2 as catalyst. Malays. J. Anal.
43. Pattanaik BP and Misra RD. Effect of reaction pathway and operating parameters on the
deoxygenation of vegetable oils to produce diesel range hydrocarbon fuels: A review. Renew. Sus. Ener.
44. Snåre M, Kubičková I, Mäki-Arvela P, Chichova D, Eränen K and Murzin DY. Catalytic deoxygenation of
unsaturated renewable feedstocks for production of diesel fuel hydrocarbons. Fuel. 87(6):933-45 (2008).
45. Yang L, Ruess GL and Carreon MA. Cu, Al and Ga based metal organic framework catalysts for the
46. Ahmadi M, Nambo A, Jasinski JB, Ratnasamy P and Carreon MA. Decarboxylation of oleic acid over Pt
catalysts supported on small-pore zeolites and hydrotalcite. Catal. Sci.Tech. 5(1):380-8 (2015).
48. Griffin MB, Ferguson GA, Ruddy DA, Biddy MJ, Beckham GT and Schaidle JA. Role of the Support and
Accepted Article
Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO2 Catalysts. ACS
49. Olbrich W, Boscagli C, Raffelt K, Zang H, Dahmen N and Sauer J. Catalytic hydrodeoxygenation of
pyrolysis oil over nickel-based catalysts under H2/CO2 atmosphere. Sus. Chem. Proces. 4(1):9 (2016).
50. Yakovlev VA, Khromova SA, Sherstyuk OV, Dundich VO, Ermakov DY, Novopashina VM, Lebedev MY,
Bulavchenko O and Parmon VN. Development of new catalytic systems for upgraded bio-fuels
51. Shi H, Chen J, Yang Y and Tian S. Catalytic deoxygenation of methyl laurate as a model compound to
hydrocarbons on nickel phosphide catalysts: Remarkable support effect. Fuel Proces. Tech.
52. Kaewmeesri R, Srifa A, Itthibenchapong V and Faungnawakij K. Deoxygenation of Waste Chicken Fats
to Green Diesel over Ni/Al2O3: Effect of Water and Free Fatty Acid Content. Energy & Fuels. 29(2):833-40
(2015).
53. Fréty R, Santos MR, Sales RF, Silva AOS, Barbosa CBM and Pacheco JGA. Flash Pyrolysis of Oleic Acid
as a Model Compound Adsorbed on Supported Nickel Catalysts for Biofuel Production. J. Braz. Chem.
54. Pandey D and Deo G. Effect of support on the catalytic activity of supported Ni–Fe catalysts for the
55. Yang C, Li R, Cui C, Liu S, Qiu Q, Ding Y, Wu Y and Zhang B. Catalytic hydroprocessing of microalgae-
57. Stakheev AY and Kustov LM. Effects of the support on the morphology and electronic properties of
Accepted Article
supported metal clusters: modern concepts and progress in 1990s. Appl. Catal. A: Gen. 188(1):3-35
(1999).
58. Schoofs GR and Benziger JB. Reaction thermodynamics of hydrocarbons with nickel(100). Langmuir.
4(3):526-32 (1988).
59. Zaera F. Selectivity in hydrocarbon catalytic reforming: a surface chemistry perspective. Appl. Catal.
triglycerides and fatty acids to hydrocarbons over Ni–Al layered double hydroxide. Catal. Today.
237:136-44 (2014).
61. Rozmysłowicz B, Mäki-Arvela P and Murzin DY. Fatty Acids-Derived Fuels from Biomass via Catalytic
Deoxygenation. In: Baskar C, Baskar S, Dhillon RS, editors. Biomass Conversion: The Interface of
Biotechnology, Chemistry and Materials Science. Berlin, Heidelberg: Springer Berlin Heidelberg; 2012. p.
199-220.
62. Peng B, Yuan X, Zhao C and Lercher JA. Stabilizing Catalytic Pathways via Redundancy: Selective
63. Rogers KA and Zheng Y. Selective Deoxygenation of Biomass‐Derived Bio‐oils within Hydrogen‐
64. Na J-G, Yi BE, Kim JN, Yi KB, Park S-Y, Park J-H, Kim J-N and Ko CH. Hydrocarbon production from
performance of Ni/MgO–Al2O3 catalysts for decarboxylation of oleic acid. Catal. Today. 164(1):457-60
(2011).
Accepted Article
66. Li G, Zhang F, Chen L, Zhang C, Huang H and Li X. Highly Selective Hydrodecarbonylation of Oleic Acid
(2015).
67. Loe R, Santillan-Jimenez E, Morgan T, Sewell L, Ji Y, Jones S, Isaacs MA, Lee AF and Crocker M. Effect
of Cu and Sn promotion on the catalytic deoxygenation of model and algal lipids to fuel-like
68. Lilis H, Amani H, Ahmad Zuhairi A and Abdul Rahman M. Deoxygenation of Palmitic Acid to Produce
Diesel-like Hydrocarbons over Nickel Incorporated Cellular Foam Catalyst: A Kinetic Study. J Adv Chem
69. Galea NM, Knapp D and Ziegler T. Density functional theory studies of methane dissociation on
anode catalysts in solid-oxide fuel cells: Suggestions for coke reduction. J. Catal. 247(1):20-33 (2007).
70. Román-Martínez MC, Cazorla-Amorós D, Linares-Solano A, De Lecea CS-Mn, Yamashita H and Anpo
M. Metal-support interaction in Pt/C catalysts. Influence of the support surface chemistry and the metal
71. Perego C and Villa P. Catalyst preparation methods. Catal. Today. 34(3):281-305 (1997).
72. Hutchings GJ and Védrine JC. Heterogeneous Catalyst Preparation. In: Baerns M, editor. Basic
Principles in Applied Catalysis. Berlin, Heidelberg: Springer Berlin Heidelberg; 2004. p. 215-58..
73. Tasker SZ, Standley EA and Jamison TF. Recent advances in homogeneous nickel catalysis. Nature.
509:299 (2014).
74. Manning MP, Garmirian JE and Reid RC. Carbon deposition studies using nickel and cobalt catalysts.
77. Chatterjee A and Jensen VR. A Heterogeneous Catalyst for the Transformation of Fatty Acids to α-
78. Li W, Gao Y, Yao S, Ma D and Yan N. Effective deoxygenation of fatty acids over Ni(OAc)2 in the
79. Jeelnik M, Varma RS, Polanc S and Kocevar M. Catalyst-free reactions under solvent-free conditions:
microwave-assisted synthesis of heterocyclic hydrazones below the melting points of neat reactants.
Figure 1. Reaction mechanism for the deoxygenation of fatty acid to n-alkanes via synergetic catalysis over Ni/ZrO2
Figure 2. Reaction routes for the DO of oleic acid to alkanes over Ni/ZnO-Al2O3. Adapted from Ref.66
Figure 3. Effect of the Ni loading on the catalytic DCX reaction of stearic acid (SA). Reaction Conditions:
T = 330 °C, time = 5 h, catalyst loading = 30 mg, stearic acid loading = 0.176 mmol. In blue, conversion of stearic
Figure 4. Catalytic performances of a carbon-supported nickel catalyst (20 wt.% Ni/C) in the DCX of different
saturated fatty acids. Reaction Conditions: T = 350 °C, time = 4 h, catalyst loading = 30 mg, fatty acid
loading = 0.20 mmol. (a) correspond to the conversion of each fatty acid. (b) corresponds to the selectivity and yield
to the corresponding hydrocarbons with one carbon atom less than the original fatty acid, i.e., LA: lauric acid to
undecane (C11); myristic acid to tridecane (C13); Palmitic acid to pentadecane (C15); stearic acid to heptadecane
(C17); arachidic acid to nonadecane (C19), and behenic acid to heneicosane (C21). Results adapted from Ref.47
Figure 5. Proposed reaction route for the DO of fatty acid to n-alkanes. Adapted from the results from references 7, 14,
66
330 °C, 5 h
C18H36O2 C17H36 + CO2
% % %
1 20 wt.%Cu/ZrO2 36 23 8
2 20 wt.%Co/ZrO2 75 9 7
3 20 wt.%Ni/ZrO2 37 79 30
4 20 wt.%Cu/Al2O3 17 59 10
5 20 wt.%Ni/C 37 89 33
6 40 wt.%Ni/SiO2 54 51 28
Catalyst XSAa, Sn-C17b, S1-C17c, S∑C17d Total SC18f, SC35g, Scrackh, Sheavyi,
% % % , SC17e, % % % % %
60 wt.%Ni/SiO2 18.1 19 30 40 58 1 - 20 21
50 wt.%Ni/CrO3 12.3 48 8 3 60 - - 17 24
[a]conversion of SA, [b] s electivity to n-heptadecane, [c] selectivity to 1-heptadecene, [d] selectivity to other C17 compounds,
[e] total selectivity to C17 compounds, [f] selectivity to C18 hydrocarbons, [g] selectivity to symmetrical ketone (C35) of stearic
acid, [h] selectivity to cracking products consisting of shorter fatty acids, C10-C17 acids and shorter hydrocarbons, [i]selectivity
Ni-Al LDH N2 10 13 53
Ni-Al LDH H2 73 52 61
60
20 wt.%Ni/Al2O3 N2 9 38 48
20 wt.%Ni/Al2O3 10 Vol.%H2/N2 80 67 85
20 wt.%Ni/Al2O3 H2 81 57 84
20 wt.%Ni/C N2 19 26 50
20 wt.%Ni/C 10 Vol.%H2/N2 64 51 77 11
20 wt.%Ni/C H2 80 81 88
[a] conversion of SA, [b] selectivity to heptadecane, [c] selectivity to C10-C17 hydrocarbons
(a) conversion of stearic acid, (b) selectivity n-heptadecane, (c) selectivity to 1-heptadecene, (d) selectivity to total
Accepted Article
C17 compounds, (e) yield of total C17 compounds. Results adapted from Ref.11
S∑C17
XSA a, Sn-C17 b, S1-C17 c, YC17 e,
d
Catalyst ,
% % % %
%
5 wt.%Cu/ɣ-Al2O3 95 20 61 81 78
5 wt.%Ni/ɣ-Al2O3 60 49 10 60 36
5 wt.%Cu/WO3/ZrO2 99 7 - 7 7
temperature (260 °C), stearic acid (1.0 g), dodecane (100 mL), catalyst (0.5 g), 40 bar H2, 8 h. A = 1-octadecanol, B = cracking,
H2 Ni/ZrO2
% % % % % %
ZrO2 13 3.2 - 29 - 12
palmitic acid (1 g), dodecane (100 mL), catalyst (0.5 g), 260 °C, 12 bar H2 with a flow rate of 20 mLmin-1, 6 h.
10 wt.%Ni/MO-Al2O3 (0.2 g), H2 pressure (3.5 MPa), under stirring at 600 rpm for 6 h. Adapted from Ref.64
H2
Accepted Article
C18H36O2 C17H36 + CO2
% % % % % % %
[a] the catalyst was prepared by a proceduresimilar to that used for the preparation of MO-Al2O3 supports. [b] ɣ-Al2O3-2 was
purchased from the Sasol Company. A: 1‐Octadecanol, B: Stearyl stearate, C: Stearate, SA: stearic acid
T = 260-300 °C, time = 1.5 h, hydrogen pressure = 20 bar, catalyst loading = 30 mg, fatty acid
Accepted Article
loading = 0.20 mmol. Adapted from Ref.67
20 wt.%Ni/Al2O3 260 39 2 15
20 wt.%Ni/Al2O3 300 92 66 76
(a) conversion of stearic acid, (b) selectivity to heptadecane, (c) selectivity to C10-C17 hydrocarbons