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Catalytic decarboxylation of fatty acids to hydrocarbons over non-noble metal catalysts:

The state of the art

Anouchka Kiméné, Robert Wojcieszak, Sébastien Paul, Franck Dumeignil*

Univ. Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, F-

59000 Lille, France


*
corresponding author: franck.dumeignil@univ-lille.fr

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.

Historically, several non-noble monometallic catalysts based on Cu, Co, Ni supported on

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

fully environmentally friendly and cost-effective process.

Keywords: deoxygenation, decarboxylation, non-noble metals, fatty acids, hydrocarbon

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

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1. Introduction

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

in the recent years to produce hydrocarbons.

In parallel to DO, other undesirable reactions such as cracking, ketonization and

dehydrogenation can also occur depending on the reaction conditions. Furthermore, other

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consecutive reactions can also take place in the gas phase. For instance, CO, CO2, H2 and H2O

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

the yield in the desired hydrocarbon.

Liquid phase reactions:

Decarboxylation: R-COOH → R-H + CO2 ∆G°573 = -83.5 kJ.mol-1 (Eq. 1)

Decarbonylation: R-COOH → R’-H + CO + H2O ∆G°573 = -17.0 kJ.mol-1 (Eq. 2)

Decarbonylation: R-COOH+ H2 → R-H + CO + H2O ∆G°573 = -67.6 kJ.mol-1 (Eq. 3)

HydroDO: R-COOH+3H2 → R-CH3 + 2H2O ∆G°573 = -86.1 kJ.mol-1 (Eq. 4)

Gas phase reactions:

Methanation: CO + 3H2 ↔ CH4 + H2O ∆G°573 = -78.8 kJ.mol-1 (Eq. 5)

Methanation: CO2 + 4H2 → CH4 + 2H2O ∆G°573 = -61.2 kJ.mol-1 (Eq. 6)

Water-gas-shift: CO + H2 → CO2 + H2 ∆G°573 = -17.6 kJ.mol-1 (Eq. 7)

where, R and R’ are saturated and unsaturated alkyl chains, respectively.

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

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nature of the couple metal/support used19, 20 and, obviously, to the method of preparation.21-23

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

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temperature range from 250 to 380 °C. The pressure is chosen in order to maintain the reactants

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

to hydrocarbons can be obtained.11 Compared to the DO of saturated fatty acids, the DO of

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

obtained.44-46 Consequently, the deoxygenation pathway of unsaturated fatty acid is similar to

those of a saturated fatty acid in its second step.

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

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cracking. Therefore, for fatty acid with similar chain lengths, the difference in catalytic

performances should not be significant.

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

when envisioning large-scale applications. Therefore, the development of more affordable

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

decarboxylation of saturated fatty acids to alkanes over heterogeneous metal-based catalysts

(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

promising results. Santillan-Jimenez et al.10-11 demonstrated that the deoxygenation of stearic

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

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catalyst was not performed. Wu et al.47 studied this point in more details for the decarboxylation

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

excellent selectivity to n-heptadecane, while 5 wt.% Cu/Al2O3 showed remarkably high

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

consecutive hydrogenation of the olefin formed by decarbonylation. Stearic acid could be

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

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the same conditions (temperature, loading, substrate concentration, acidity of the supports…) and

using the same substrates.


Accepted Article
1. DCX of fatty acids over monometallic catalysts

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.

1.1.Effect of the metal nature

Recently, Wu et al.47 have screened the performances of a set of three 20 wt.%

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

they are the most commonly reported ones in the literature.49-53

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1.2.Effect of the support and the gas atmosphere

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.

First, Wu et al.47 investigated the effect of Ni and Cu supported on zirconia, alumina,

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

efficient one in the DCX reaction of stearic acid to n-heptadecane.47

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

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to C18 less than 1 %). The highest selectivity to n-heptadecane was observed with Ni/Cr2O3,

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

conversion of stearic acid, respectively and 57 and 52 % of selectivities to n-heptadecane

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

conversion,, respectively and 38 and 13 % in selectivities respectively. Under an atmosphere

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

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20 wt.%Ni/Al2O3 (81 % of conversion and 57 % of selectivity) and over Ni-Al LDH (73 % of

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

was much higher in H2 than either in H2/N2 mixtures or pure N2.30

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

selectivity to cracking products over nickel catalysts is relatively high.

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

very important parameter to control and maintain the catalytic performances.61

Berenblyum et al.19 compared the performances of 5 wt.% Ni and Cu catalysts supported on ɣ-

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

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reaction because this metal is more selective to 1-heptadecene than to n-heptadecane, while for

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

7% of selectivity to C17 hydrocarbons respectively) compared to that of the catalysts supported

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

deposition, which is responsible of the deactivation of the catalyst.

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

96 % and 93 % of selectivity to n-heptadecane, respectively. The performance of Ni/TiO2 was

slightly lower with 87 % of selectivity to n-C17 at 98 % of conversion. The lowest conversions

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

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34 % of selectivity to 1-octadecanol, while over Ni/ZrO2, Ni/CeO2 and Ni/TiO2, the selectivities

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

best catalytic performances were obtained over the Ni/ZrO2 catalyst.

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

maintain its high activity.63

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Accepted Article

Figure 1 : Reaction mechanism for the deoxygenation of fatty acid to n-alkanes via synergetic catalysis over Ni/ZrO2 in the

presence of H2. Adapted from Ref.30

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

was palmitone, derived from ketonization reaction.

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

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DCX. The catalyst calcined at 300 °C gave the best catalytic performances in the reaction

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

DCX of oleic acid.

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

MO-Al2O3 supports (incipient wetness impregnation method; catalyst denoted as Ni/ɣAl2O3-1)

and for the catalyst purchased from Sasol Company (denoted as Ni/ɣAl2O3-2) were not the same

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due their difference in term of basicity. All the catalysts tested showed total conversion of fatty

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

products such as octadecanal and octadecanol were formed by hydrogenolysis. Besides,

octadecane was formed in low amounts.

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.

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In addition, it was observed that the Al2O3 support exhibits a decarboxylation activity, which

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).

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The effect of the metal loading on the reaction of DO of fatty acids to n-alkanes was

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

must be facilitated due to the large exposed nickel surface.30, 62

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

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almost the same for the 10 wt.% and 30 wt.%Ni/C catalysts. The 30 wt.%Ni/C catalyst showed

the highest yield to n-heptadecane.


Accepted Article

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

acid, in orange selectivity to n-heptadecane. Adapted from Ref.47

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.

1.4.Influence of the chain length of the saturated fatty acid

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Wu et al.47 investigated the DCX of different saturated fatty acids (C12 to C22) over a

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

and under the same reaction conditions.

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Accepted Article

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

1.5.Solvent-free fatty acid DO

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-

pentadecene. Depending on the reaction conditions, the concentration in n-pentadecane was,

more or less, higher than that of n-pentadecene. In fact, the authors reported that the DCX

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reaction was more pronounced in the first 3 h of reaction, while the DCN reaction dominated at

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).

2. Decarboxylation of fatty acids over bimetallic catalysts

In order to improve the catalytic performances of a 20 wt.%Ni/Al2O3 catalyst, Loe et al.67

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

conversion increased from 92 % over 20 wt.%Ni/Al2O3 to 98 % over 20 wt.%Ni-5 wt.%

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

3. DCX of fatty acids over trimetallic catalysts

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In order to develop a cost-effective catalyst for the DO reaction, Chiam et al.42 decided to

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,

three isomers of n-pentadecane (2,5-dimethyltridecane, 4,8-dimethyltridecane and 2,7,10-

trimethyldodecane) were formed as well as n-pentadecene and its isomers (1,4,6,8-

tetramethylundecene). Thus, NiSnK/SiO2 was found to decarboxylate PA to n-pentadecane with

some DCN and isomerization products. Unfortunately, the selectivities to C15 were not reported

in this paper.42

4. Reaction pathway

As illustrated by several studies in the literature, the catalytic DO pathway largely

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

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final hydrocarbon is obtained.44-46 Consequently, the DO pathway of unsaturated fatty acids is

similar than that of the second step of DO of saturated fatty acids.


Accepted Article

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,

ketonization and cracking as well as other consecutive reactions, such as isomerization,

dehydrogenation, hydrogenation, cyclisation and dimerization were also observed. Cracking

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

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corresponding saturated fatty acid (for example, hydrogenation of oleic acid to stearic acid).

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

such as diunsaturated acids, triunsaturated acids as well as aromatics.44 Furthermore, compared to

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

highly unsaturated coumpounds.13, 39, 40

4. Main challenges and perspectives

The decarboxylation of fatty acid on non-noble based catalysts is still a challenge.

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,

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the DO of stearic acid under inert atmosphere or low hydrogen quantity (5% or 10% H2/N2)

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

cracking. Furthermore, the decarboxylation reaction should be studied in high-pressure semi-

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

would be a main challenge.

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Conclusions

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

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Acknowledgements

This work was supported by Weylchem. The authors would like to thank Dr. Olivier Simon and

Mrs. Claire Durlin for their collaboration and fruitful discussions.


Accepted Article
Chevreul Institute (FR 2638), Ministère de l’Enseignement Supérieur et de la Recherche, Région

Hauts-de-France and FEDER are acknowledged for supporting and funding partially this work.

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Accepted Article
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Figures Captions:

Figure 1. Reaction mechanism for the deoxygenation of fatty acid to n-alkanes via synergetic catalysis over Ni/ZrO2

in the presence of H2. Adapted from Ref.30


Accepted Article

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

acid, in orange selectivity to n-heptadecane. Adapted from Ref.47

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

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Table 1: Performances of monometallic catalysts in the DCX of stearic acid (SA). Reaction conditions:
Accepted Article
T = 330 °C, time = 5 h, micro-batch reactor: 1,67 mL, inert atmosphere, catalyst loading = 30 mg, SA

amount = 0.176 mmol. Adapted from Ref.47

330 °C, 5 h
C18H36O2 C17H36 + CO2

Entry Catalyst XSAa, XC17b, YC17c,

% % %

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

(a) Conversion of SA, (b) selectivity to n-heptadecane, (c) yield of n-heptadecane.

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Table 2: Performances of a series of Ni catalysts in the DCX of SA to n-heptadecane. Reaction conditions: mSA = 4.5 g,
Accepted Article
mdodecane = 86 g, catalyst loading = 1 g, T = 300 °C, P = 6 bar, t=6h, Fcarrier gas = 25 mL/min (He). Adapted from Ref.14

Catalyst XSAa, Sn-C17b, S1-C17c, S∑C17d Total SC18f, SC35g, Scrackh, Sheavyi,

% % % , SC17e, % % % % %

81 wt.% Raney-Ni 14 30 13 7 50 <0.5 - 17 32

16 wt.%Ni/Al2O3 17.8 29 12 4 46 <0.5 12 13 29

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

to dimeric products [-] product was not formed.

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Table 3: Results of DO of SA over Ni catalysts under various gas compositions. Reaction Conditions: mSA = 1.75 g,
Accepted Article
mdodecane = 25 g, catalyst loading = 0.5 g, T = 300 °C, P = 9.3 bar, time = 1.5 h, Fcarrier gas = 70 mL/min.

300 °C, 1.5 h

C18H36O2 C17H36 + CO2

XSA a, SC17 b, SC10-C17 c,


Catalyst Gas atm. Ref.
% % %

Ni-Al LDH N2 10 13 53

Ni-Al LDH 10 Vol.%H2/N2 42 30 43

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

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Table 4: DO of stearic acid. Reaction conditions: T = 350 °C, time = 6 h, Pressure = 14 bar, atmosphere: hydrogen.

(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

350 °C, 14 bar H2, 6 h

C18H36O2 C17H36 + CO2

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

5 wt.%Ni/WO3/ZrO2 100 10 0.6 11 11

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Table 5: DCX of stearic acid over nickel-based catalyst supported on different supports. Reaction conditions:

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,

C = stearyl stearate. Results adapted from Ref.62


Accepted Article

H2 Ni/ZrO2

C18H36O2 C18H36O C17H36 + CO

Catalyst XSA, Sn-C17, Sn-C18, SA , SB , SC ,

% % % % % %

ZrO2 13 3.2 - 29 - 12

3 wt.%Ni/ZrO2 96 51 2.5 33 3.4 7.6

5 wt.%Ni/ZrO2 100 90 2 6.7 1 -

10 wt.%Ni/ZrO2 100 96 1.5 1.2 1.2 -

15 wt.%Ni/ZrO2 100 96 1.5 1.4 1.3 -

10 wt.%Ni/TiO2 98 87 5 6.7 0.9 0.7

10 wt.%Ni/CeO2 100 93 0.4 3.5 2.8 -

10 wt.%Ni/Al2O3 63 81 0.7 14 0.9 3.5

10 wt.%Ni/SiO2 45 57 1.5 34 1.3 5.8

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Table 6: DO of palmitic acid over nickel-based catalyst supported on different supports. Reaction conditions:

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.

Results adapted from Ref.30


Accepted Article
H2 Ni/ZrO2

C16H32O2 C16H32O C15H32 + CO

Catalyst XPA,% Sn- Siso- Sn- Siso- SA SB SC

C15,% C15,% C16,% C16,% ,% ,% ,%

ZrO2 6.2 3.1 - 0.9 - - 18 7.6

3 wt.%Ni/ZrO2 67 55 - 2 - 2.5 32 5.8

5 wt.%Ni/ZrO2 100 90 - 0.8 - 9 - -

10 wt.%Ni/ZrO2 100 85 - 0.7 - 14 - -

5 wt.%Ni/ZrO2 100 83 - 0.7 - 17 - -

15 wt.%Ni/Al2O3 51 74 - 1.5 - 6.8 15 3.2

5 wt.%Ni/SiO2 41 59 - 0.7 - 5.3 33 2.3

5 wt.%Ni/HBEA 100 24 4.8 49 16 6 - -

5 wt.%Ni/HZSM-5 100 21 2.1 59 13 4.9 - -

A: Lighter alkanes, B: 1-hexadecanol, C: palmityl palmitate.

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Table 7: DO of oleic acid over Ni/MO-Al2O3 catalysts at 280 °C. Reaction conditions: oleic acid (2.0 g), decalin (30.0 g),

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

Catalyst XOA, Sn-C17, Sn-C18, SA, SSA, SB, SC,

% % % % % % %

Ni-MgO-Al2O3 100 23.5 3.3 5.7 1.5 - 66

Ni-CaO-Al2O3 100 8.3 2.4 10.3 4.8 - 74.2

Ni-NiO-Al2O3 100 93.2 2.7 - - - 4.1

Ni-CuO-Al2O3 100 93.8 1.3 - - - 4.9

Ni-ZnO-Al2O3 100 94.5 4.3 1.2 - - -

Ni-ɣAl2O3-1 a 100 57.6 1.6 1.6 4.7 34.8 -

Ni-ɣAl2O3-2 b 100 81.4 2.6 1 - 16 -

[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

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Table 8: DO of stearic acid over alumina-supported Sn- and Cu-doped Ni/Al2O3 catalysts. Reaction Conditions:

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

C18H36O2 + H2 C17H36 + CO2

Catalyst T XSA a SC17 b SC10-C17 c

(°C) (%) (%) (%)

20 wt.%Ni/Al2O3 260 39 2 15

20 wt.%Ni–5 wt.%Cu/Al2O3 260 54 7 13

20 wt.%Ni–1 wt.%Sn/Al2O3 260 30 3 7

20 wt.%Ni/Al2O3 300 92 66 76

20 wt.%Ni–5 wt.%Cu/Al2O3 300 98 79 86

20 wt.%Ni–1 wt.%Sn/Al2O3 300 39 17 23

(a) conversion of stearic acid, (b) selectivity to heptadecane, (c) selectivity to C10-C17 hydrocarbons

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