Renewable and Sustainable Energy Reviews 111 (2019) 303–313

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Renewable and Sustainable Energy Reviews

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Green diesel production from upgrading of cashew nut shell liquid T

∗
C.A. Scaldaferri, V.M.D. Pasa
Universidade Federal de Minas Gerais, Departamento de Química, Laboratório de Combustíveis, 6627 Antônio Carlos Ave, Belo Horizonte, MG, 31270-901, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: In recent years, there has been a strong global interest in developing technologies for converting renewable and
Cashew nut shell liquid low-cost raw materials into green diesel and bio-jet fuel, which are made of hydrocarbons. In this work, cashew
Deoxygenation nut shell liquid (CNSL), which is an industrial waste, was used as a feedstock to produce green diesel. Different
Hydrogenation reaction conditions during the upgrading process (deoxygenation, hydrogenation and cracking) were evaluated
Upgrading
using palladium over activated charcoal (Pd/C) as a catalyst. The catalyst was characterized by X-ray diffraction
Green diesel
Biofuels
and specific surface area analysis. The influences of the reaction parameters, such as temperature (180, 250 and
300 °C), time (5 and 10 h) and pressure (10, 20, 30 and 40 bar), were investigated using 10% w/w Pd/C. The
composition of the products was determined using gas chromatography coupled with mass spectrometry and
infrared spectroscopy. Higher pressures and temperatures led to a higher degree of deoxygenation and hydro-
genation. In contrast, lower pressures or temperatures resulted in higher degrees of cracking. From the opti-
mization experiments, a 98% yield of hydrocarbons corresponding to the diesel range was obtained under a
40 bar H2 atmosphere at 300 °C, 10 h, and 500 rpm (in a batch reactor). Of these hydrocarbons, 89% were
saturated alkanes, 3% were aromatic compounds and 6% were oxygenated compounds. This new and sustain-
able route is promising because it involves the conversion of a low-value residue into green diesel using mild
experimental conditions. Biofuel production from CNSL allows the total valorization of the residues in the
cashew-nut agroindustrial chain and has potential industrial applications in many countries.

1. Introduction
The world population has increased exponentially and reached ap-
proximately 7.7 billion people in 2018 [1,2]. This increase has a direct
influence on energy demand and environmental problems. One of the
main reasons for energy consumption is transportation activity, which
connects people and transports merchandise between different points in
a unique global market [2–4]. Oil remains the most commonly used
energy source, with a consumption equivalent to approximately 90
million barrels per day [3]. Diesel, gasoline, and bio-jet fuel are the
main fossil fuels used, and these sources need to be gradually sub-
stituted by renewable fuels to ensure that future generations are not
bequeathed a planet that is impossible to inhabit [4,5].
Decarbonization of the planet represents a substantial challenge for
society, and an important key is to reduce CO2 emissions, which are
associated with increased climate change. The development of sus-
tainable technologies, such as the production of biofuels, provides a
relevant renewable alternative to fossil fuels. In addition, the growing
demand for energy, a gradual decline in petroleum-based resources and
unstable prices have stimulated the use of biofuels in the transport
sector [6–8].
One of the major trends in the area of renewable fuels is related to
the production of drop-in biofuels, which have no oxygen in their
composition and are analogous to those from petrochemical sources.
Drop-in biofuels are essentially composed of biohydrocarbons whose
structures contain carbon chains of a size similar to those in fossil fuels.
These biofuels have been particularly attractive as substitutes for jet
fuel and petroleum diesel and are called bio-jet fuel or biokerosene and
green diesel, respectively [9,10]. Drop-in biofuels are not hygroscopic
and have higher heats of combustion than oxygenated biofuels, such as
bioethanol and biodiesel. As a consequence, drop-in biofuels can be
used in higher contents in blends with fossil fuels and can share facil-
ities for the storage and distribution of fossil fuels [11,12].
The main challenges in the development of drop-in biofuels are the
production costs and the high cost of the feedstock, which represents
approximately 60–80% of the final cost, depending on the processing
route [12,13]. Thus, the search for renewable and low-cost raw mate-
rials for the sustainable production of biohydrocarbons is of funda-
mental importance for the inclusion of these liquid biofuels in the
market. In an attempt to produce biohydrocarbons at competitive costs,
there is a growing interest in low-value residual materials that are not
considered to be agricultural commodities, are not competitive with

∗
Corresponding author.
E-mail address: vmdpasa@gmail.com (V.M.D. Pasa).

https://doi.org/10.1016/j.rser.2019.04.057
Received 22 October 2018; Received in revised form 17 April 2019; Accepted 18 April 2019
Available online 18 May 2019
1364-0321/ © 2019 Elsevier Ltd. All rights reserved.
C.A. Scaldaferri and V.M.D. Pasa Renewable and Sustainable Energy Reviews 111 (2019) 303–313

Nomenclature H2 hydrogen
N2 nitrogen
A Abbreviations OCH3 methoxyl
Pd/C palladium over activated charcoal
Abbreviations Pt platinum
Ru ruthenium
B5 blend of 5% of biodiesel in diesel Rh rhodium
B10 blend of 10% of biodiesel in diesel TG thermogravimetric
BET Brunauer, Emmett and Teller TGA thermogravimetric analysis
BJH Barrett-Joyner-Halenda rpm rotations per minutes
CNSL cashew nut shell liquid h hours
CO carbon monoxide min minutes
CO2 carbon dioxide °C degree celsius
C9 hydrocarbons with nine carbons kg kilogram
C14 hydrocarbons with fourteen carbons mL mililiters
C15 hydrocarbons with fifteen carbons μL microliters
C20 hydrocarbons with twenty carbons Å angstron
C21 hydrocarbons with twenty-one carbons m meter
DTG thermogravimetric derived mm milimeters
XRD X-rays diffraction cm/s centimeters per seconds
FAO Food and Agriculture Organization m2/g square meter per gram
FTIR fourier-transform infrared spectroscopy w weigth
GC-MS gas chromatograph-mass spectrometer
H2O water

food, and are highly sustainable [12–14]. This work represents a unique nuclei into cycloparaffins.
contribution to the development of green technologies based on re- Biofuel upgrading processes have been extensively studied in the
sidual raw materials by using cashew nut shell liquid (CNSL), which has literature, and a variety of catalysts have been tested in deoxygenation
a low cost and can make the production of drop-in fuels feasible, mainly and hydrogenation reactions. Among the various types of catalysts,
in regions of the world that produce cashew nuts on a large scale. materials based on noble metals, such as Ru, Rh, Pd and Pt, are most
Therefore, the use of CNSL as a renewable source of hydrocarbons can efficient for deoxygenation reactions at temperatures between 250 and
lead to sustainable processes in the fuel industry. 450 °C and hydrogen pressures from 10 to 300 bar, depending on the
CNSL is a byproduct of the cashew kernel industry and is produced reactor configuration [26–29]. The use of hydrogen at a high pressure
by Anacardium occidentale, commonly known as the cashew tree. In the can lead to high process costs, and this fact has stimulated investiga-
inner part of the cashew nut, there is a kernel, which makes up the tions on low-pressure conversion routes, as presented in this work.
edible part of the nut. The external part of the cashew nut (shell) In the present study, the upgrading of CNSL was carried out with the
contains the mesocarp, which is filled with a dark liquid, CNSL. CNSL aim of producing green diesel via simultaneous deoxygenation and
accounts for 20–25% of the nut's weight and can be extracted by dif- hydrogenation reactions over a conventional catalyst (Pd/C) using mild
ferent methods, such as cold pressing, solvent extraction and thermo- conditions. A study of experimental reaction conditions was performed
mechanical processes. In extraction processes, the outer shell ruptures to optimize the yields of saturated and nonoxygenated compounds in
and releases the alkylphenols present in the porous shell (mesocarp), the diesel range, which can also be used in low contents in blends with
which are the compounds of CNSL [15–20]. aviation kerosene [30]. This work is the first study to investigate the
CNSL is an inedible feedstock rich in substituted phenols, including conversion of CNSL to drop-in biofuels composed of biohydrocarbons.
anacardic acid, cardanol, cardol and 2-methyl cardol [16,20–22] This renewable fuel presents an interesting composition based mostly
(Fig. 1), whose structures are noteworthy, having 15-carbon chains and on cycloalkanes, which improve the cold properties of fuels. It is im-
representing an interesting source for obtaining hydrocarbons and portant to emphasize that the proposed route involves the transfor-
cyclic compounds, particularly in the range of aviation kerosene (C9- mation of a low-cost waste into biofuel, resulting in a process that is
C15) and diesel oil (C15-C21) [23–25]. At temperatures above 180 °C,
anacardic acid undergoes a decarboxylation reaction and is converted
into cardanol, thus producing technical-grade CNSL. The oil contains
68–95% cardanol, 3.8–19% cardol, 1.2–4.1% 2-methyl cardol and
1.1–1.8% anacardic acid [16].
CNSL contains a large amount of oxygen due to phenolic con-
stituents in its composition, which results in thermal and chemical in-
stability in fuels produced with this residual liquid [10]. Furthermore,
the presence of oxygenated compounds in the fuels results in a hygro-
scopic character, consequently promoting the proliferation of micro-
organisms in storage tanks, leading to oxidation and polymerization of
fuels, mainly in diesel oil [11]. Thus, catalytic deoxygenation processes
are required to produce fuels with superior properties from CNSL. In
addition, the presence of a high content of aromatic compounds in the
fuel composition can cause problems in combustion as a result of the
formation of soot. Therefore, hydrogenation is also an important up-
grading reaction to be performed and studied to convert the aromatic Fig. 1. Main constituents of cashew nut shell liquid, R = C15H25-31.

304
C.A. Scaldaferri and V.M.D. Pasa
more inexpensive than those that use triglycerides from vegetable oils.
Furthermore, CNSL is a nonfood feedstock and therefore does not
compromise food security. This material does not require more area for
planting, water, soil nutrients, or pesticides. As a consequence, CNSL is
highly sustainable and has social, economic and environmental bene-
fits.
2. Materials and methods
2.1. Feedstock characterization
CNSL was supplied by the Brazilian company Resibras, Fortaleza,
Ceará, Brazil. CNSL extraction was accomplished by a thermo-
mechanical process. In this process, the nuts were roasted at approxi-
mately 215 °C. Under these conditions, the outer shell ruptures and
releases the CNSL from the porous shell (mesocarp), followed by the
removal of the inner shell, which allows nut recovery.
The CNSL was characterized by Fourier transform infrared spec-
troscopy (FTIR) and thermogravimetric analysis (TGA). For the char-
acterization of the main groups present in the CNSL sample, FTIR
spectra were obtained by using an ABB Bomem_MB Series ARIS-ZONE
spectrophotometer with 16 scans and 4 cm−1 resolution in a diamond
cell. The TG/DTG thermogravimetric curves were obtained in a TA Q50
instrument in the temperature range of 35–800 °C using a heating rate
of 10 °C min−1 and N2 atmosphere with a flow rate of 60 mL min−1.
2.2. Catalyst characterization
Palladium supported on activated charcoal (Pd/C), 5% by weight
(w/w), was purchased from Sigma Aldrich®. Pd/C catalyst was char-
acterized in an X-ray diffractometer (Shimadzu XRD-6000) operated at
40 KV and 30 mA using Cu-Kα1 radiation (λ = 1.5406 Å). The 2θ range
was from 5 to 60°, and the scanning speed was 0.02° s−1. The catalyst
surface area was measured by N2 physisorption on a Micrometrics ASAP
2020. The catalyst was degassed for 6 h at 200 °C prior to the analysis.
Surface areas were measured by the BET method (Brunauer, Emmett
and Teller), and the pore diameter and volume were calculated by the
BJH method (Barrett-Joyner-Halenda) using the Quantachrome ASi
Qwin 2.0 software.
2.3. Upgrading reactions
The performance of the Pd/C catalyst was evaluated in the up-
grading reactions (deoxygenation, hydrogenation and cracking) of
CNSL under a H2 atmosphere and under different reaction conditions.
First, the Pd/C catalyst was pretreated using a 5% H2/N2 mixture with a
50 mL min−1 flow rate in a tubular oven for 2 h at 250 °C to ensure that
the palladium was in reduced form immediately before the reaction.
Various reaction temperatures (180, 250 and 300 °C), H2 pressures (10,
20, 30 and 40 bar) and reaction times (5 and 10 h) were tested. In all
experiments, a 10% (w/w) catalyst/mass ratio and 500 rpm were used.
A summary of the experimental conditions and the code associated with
each reaction are presented in Table 1. All experiments were conducted
in batch mode in a Parr reactor (model 4348) with a capacity of
100 mL. After each reaction, the product was centrifuged at 700 rpm to
separate the catalyst.
2.4. Determination of product composition
The major components of the upgrading products were determined
using a Shimadzu model QP5050 gas chromatograph coupled to a mass
spectrometer (GC-MS) in the electronic impact ionization mode.
Analysis was performed using a Pona 100, 100 m × 0.25 mm column
and temperature program starting at 50 °C for 10 min, heating at 2.5 °C
min−1 to 185 °C, followed by heating at the rate of 5 °C min−1 to
250 °C, where the temperature was maintained for 20 min. The injector
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Renewable and Sustainable Energy Reviews 111 (2019) 303–313
and detector temperatures were 280 °C and 260 °C, respectively.
Helium was used as the carrier gas, with a linear velocity of
17.7 cm s−1. The injected volume was 1 μL, and the split ratio was 1/
50. The compounds present in the products were identified by com-
paring the mass spectra of the investigated species with the spectra of
the Wiley and NIST libraries, considering similarities above 85% using
Shimadzu's GCMS Solution software. The results were treated by means
of semi-quantification of the main constituents, evaluating the relative
area percentage of the main peaks and performing the normalization of
the total component content. In addition to GC-MS analysis, the pro-
ducts were characterized by FTIR.
3. Results and discussion
3.1. Feedstock characterization
Absorption bands in the infrared spectra, characteristic of the che-
mical groups present in the CNSL, are shown in Fig. 2. The presence of
the OH group, which is related to the phenolic structure of the CNSL, is
indicated by the absorption band at 3338 cm−1, which might also have
a contribution of dissolved water in the sample. A weak band char-
acteristic of C-H stretching of the sp2 carbon, and associated with the
presence of unsaturation in the aliphatic chains was observed at
3007 cm−1. The bands centered at 2920 cm−1 and 2860 cm−1, re-
spectively, are related to the asymmetrical and symmetrical stretching
of the methyl and methylene groups (CH3 and CH2) of the saturated
aliphatic chains. The presence of aromatic compounds was indicated by
the absorption bands at 1587 cm−1 and 1452 cm−1, which are attrib-
uted to C]C stretching vibrations of the aromatic ring. The absorption
bands at 1263 cm−1and 1168 cm−1, attributed to the C-O stretch of the
phenol ring, and to the deformation of the OH group, respectively,
confirmed the phenolic nature of the sample [31]. A band at
1710 cm−1, assigned to the carboxyl group (COOH), was not observed,
which means that the CNSL used did not contain anacardic acid. Thus,
the sample of CNSL underwent decarboxylation, in which the anacardic
acid was converted to cardanol as a consequence of CO2 loss. This result
was expected as a consequence of the cashew nut thermal treatment at
215 °C.
TG/DTG analysis was carried out to determine the temperature
range for performing the CNSL upgrading reactions. The thermal de-
composition curve for the CNSL under a nitrogen atmosphere is pre-
sented in Fig. 3. The CNSL decomposition occurred over a wide tem-
perature range, presenting thermal stability up to 180 °C and two
regions of degradation. The first event is centered at 255 °C and the
second, with overlapping of multiple events, is centered between 440
and 480 °C. The first event occurred between 180 and 300 °C, and the
maximum degradation temperature was at 255 °C, corresponding to a
mass loss of 70%. This loss can be attributed to the decomposition of the
CNSL aliphatic chain, C15H25-31, which has a molar mass between 205
and 211 g mol−1 and corresponds to 70% of the cardanol mass
Table 1
Identification codes for the reactions and the experimental conditions for the
CNSL upgrading under H2 atmosphere.
Reaction Temperature (°C) Time (h) H2 pressure (bar)
A 180 10 20
B 250 10 20
C 300 5 20
D 300 10 20
E 300 10 10
F 300 10 30
G 300 10 40
H 300 5 10
H* 300 5 10
H* reaction performed without catalyst.
C.A. Scaldaferri and V.M.D. Pasa
Fig. 2. FTIR spectrum of the CNSL.
Fig. 3. TG-DTG curves for the CNSL at a rate of 10 °C min−1 and a flow rate of
N2.
(300 g mol−1) [16]. The second event was observed between 420 and
550 °C, and it is related to a mass loss of 30%. It can be associated with
the phenol nuclei degradation. The results confirmed the information
extracted from the FTIR spectrum, indicating that the CNSL used is
composed predominantly of cardanol.
3.2. Catalyst characterization
In the X-ray diffractogram (XRD) of Pd/C catalyst (Fig. 4), the
amorphous character of the charcoal can be observed through the
presence of the wide band around 23°. The peaks centered at 2θ = 40,
47.5 and 68° are characteristic of palladium and are of low intensity,
possibly due to the small number of metallic particles supported on the
charcoal. Peak profiles indicated a good dispersion of the metal on the
support, a characteristic that contributes to a greater catalyst activity
[32–34].
From the adsorption and desorption isotherms (Fig. 5a) was ob-
served an expressive presence of micropores in the Pd/C catalyst due to
the large volume of gas adsorbed at low pressures (up to 0.3). The
catalyst presented a high specific surface area calculated by the BET
method (1068 m2 g−1). This result was consistent with the values
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Renewable and Sustainable Energy Reviews 111 (2019) 303–313
reported by Mäki-Arvela et al. [34] whose studies confirmed surface
areas between 715 and 1126 m2 g−1 for this type of material. The
presence of hysteresis in the isotherm indicated the existence of me-
sopores. Mesopores had diameters predominantly between 36 and 70 Å
according to the distribution of the pore size measured by the BJH
method (Fig. 5b).
3.3. Evaluation of upgrading reactions
3.3.1. Catalytic activity of the Pd/C catalyst
Table 2 shows the degree of deoxygenation, the degree of hydro-
genation and the degree of cracking of the CNSL from the reactions
performed without catalyst (H*) and using Pd/C (H). These aspects of
the Pd/C catalytic activity were evaluated according to the distribution
of compounds in the products obtained from these two reactions at
300 °C, 10 bar H2, 5 h and 500 rpm. The distribution of compounds was
based on the yield of cycloalkanes, alkanes, oxygenated alkanes, aro-
matic hydrocarbons and phenols, as presented in supplementary ma-
terial S1.
The degree of deoxygenation for the catalyzed reaction was lower
(36%) than that of the noncatalyzed reaction (67%); however, this re-
sult occurred since Pd/C simultaneously takes part in deoxygenation
and hydrogenation reactions, thus resulting in a notable degree of hy-
drogenation (16%). For the noncatalyzed reaction, no hydrogenation
reaction was observed. When producing cycloalkanes and/or n-alkanes,
hydrogenation reactions are fundamental for obtaining the compounds,
and hydrogenation appears to be a preliminary step to deoxygenation
reactions over Pd/C catalysts, as discussed in section 3.4. For both re-
actions, a similar degree of cracking was observed (22% for the reaction
without catalyst and 18% for the reaction with Pd/C) as a result of the
cracking of the aliphatic chains present in CNSL.
The results presented in Table 2 confirm that the catalyst under
study is essential for obtaining cyclic alkanes from hydrogenation re-
actions. However, the deoxygenation reactions occurred to a limited
degree due to low hydrogen pressure, as the amount of H2 was not
sufficient to hydrogenate the aromatic nuclei and to drive deoxygena-
tion. Therefore, the catalyzed reactions were performed under a higher
H2 pressure.
3.3.2. Product distribution according to reaction conditions
To evaluate the performance of Pd/C in CNSL upgrading at higher
H2 pressures, reactions at 10, 20, 30 and 40 bar H2 were carried out.
The total-ion chromatograms of the products illustrate the distribution
Fig. 4. X-ray diffractogram of 5% Pd/C catalyst.
C.A. Scaldaferri and V.M.D. Pasa Renewable and Sustainable Energy Reviews 111 (2019) 303–313

Fig. 5. a) N2 adsorption/desorption isotherms and b) pore size distribution of the Pd/C catalyst.

Table 2 and 12% aromatic compounds, 9% oxygenated cycloalkanes and 16%

Degree of deoxygenation, degree of hydrogenation and degree of cracking of linear alkanes were produced at 300 °C (D, Table 3).
the CNSL from the reaction without catalyst and using Pd/C, at 300 °C, under The results demonstrate the influence of temperature on the deox-
10 bar H2, 5 h and 500 rpm. ygenation, hydrogenation and cracking reactions of CNSL.
Deoxygenation degree Hydrogenation degree Cracking degree Deoxygenation and cracking reactions were observed to a greater ex-
(%) (%) (%) tent at 300 °C than at 250 °C. At 300 °C, a yield of 9% oxygenated
compounds and 18% alkanes was observed, and at 250 °C, 27% oxy-
No catalyst 67 0 22
Pd/C 36 16 18
genated compounds and 1% alkanes were observed. However, a lower
degree of hydrogenation was observed at 300 °C (12% aromatics) than
at 250 °C (1% aromatic compounds), as hydrogenation reactions are
of compounds formed in the reactions. Fig. 6 shows the product chro- exothermic and therefore are favored at lower temperatures.
matograms obtained from these reactions. The results (Fig. 6) show that
the intensities of the peaks with retention times higher than 130 min
(CNSL compounds) decreased with increasing H2 pressure, resulting in
a higher deoxygenation efficiency. In supplementary material S2, the
product chromatograms obtained at different reaction temperatures
(180, 250 and 300 °C) at 20 bar H2, 10 h and 500 rpm are presented.
From the latter chromatograms, it can be observed that higher tem-
peratures led to a higher degree of deoxygenation.
Table 3 shows the composition of the products obtained under
various reaction conditions, including temperature (180, 250 and
300 °C), time (5 and 10 h) and pressure (10, 20, 30 and 40 bar), based
on GC-MS analyses. According to the product distribution, the main
products observed throughout the conversion of CNSL (cardanol) were
linear alkanes ranging from C14 to C20 (tetradecane, pentadecane,
heptadecane, octadecane and eicosane), pentadecylcyclohexane, 3-
pentadecylcyclohex-1-one and pentadecylbenzene. The presence of
compounds resulting from the cracking of the aliphatic chains present
in the CNSL structure, which are predominantly in the diesel fuel range
(C15 to C21), was observed, especially when a low H2 pressure was
used (see Table 3).
Fig. 7 presents the percentages of each class of compounds (phenols,
aromatic hydrocarbons, oxygenated cycloalkanes, cycloalkanes and
alkanes) relative to the total constituent percentage in the products
obtained at different reaction temperatures and pressures.
According to the product distribution obtained as a function of
temperature (Fig. 7a), an increase in temperature from 180 to 250 °C
led to a decrease in the percentage of phenols, signaling that the
deoxygenation and hydrogenation reactions are favored at higher
temperatures. As a consequence, the increase in temperature led to
higher cycloalkane yields, 12% at 180 °C and 67% at 250 °C (products A Fig. 6. Total-ion chromatograms of products E (10 bar H2), D (20 bar H2), F
and B, respectively, Table 3). In the deoxygenation and hydrogenation (30 bar H2) and G (40 bar H2) obtained at 300 °C over a 10 h period. *Refers to
reactions at 250 and 300 °C, 27% oxygenated cycloalkanes, 1% aro- cyclic compounds, where C21H36O corresponds to cardanol, the main con-
matic compounds and 1% linear alkanes were obtained at 250 °C (B), stituent of CNSL.

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Table 3
Chemical formulas, names, chemical structures and relative percentages of the compounds obtained in each reaction (A-G), based on GC-MS analysis.
Formula Compound/Structure Content (%)

A B C D E F G

180 °C 250 °C 300 °C 300 °C 300 °C 300 °C 300 °C

10 h 10 h 5h 10 h 10 h 10 h 10 h
20 bar H2 20 bar H2 20 bar H2 20 bar H2 10 bar H2 30 bar H2 40 bar H2

*C21H36O 28 4 15 14 30 6 2

*C21H42O 18 27 13 9 16 5 6

*C21H36 20 1 11 12 23 6 3

*C21H42 12 67 44 47 10 67 79

C20H42 7 1 6 6 7 4 3

C18H38 3 – – – 3 – –

C17H36 4 – 5 4 3 3 3

C15H32 3 – 3 4 3 2 2

C14H30 3 – 1 2 3 – –

Others – 2 – 2 2 2 2 2

The influence of pressure on CNSL conversion into different com-
pounds is shown in Fig. 7.b. The amount of H2 used in the reaction is
significant in CNSL conversion into saturated hydrocarbons. With an
increase in pressure, a decrease in the content of phenolic and aromatic
compounds, as well as the alkanes content from thermal cracking of
aliphatic chains, was observed. The reaction with 10 bar H2 did not
have sufficient H2 to achieve the hydrogenation of phenols to a sub-
stantial extent. On the other hand, a conversion of 98% of the phenolic
fraction into aromatic hydrocarbons (3%), alkanes (10%), oxygenated
cycloalkanes (6%) and cycloalkanes (79%) could be observed using
40 bar H2 pressure (product G, Table 3), as shown in Fig. 7.b. The re-
sults indicated that increased pressure favored deoxygenation and hy-
drogenation reactions, resulting in higher yields of cycloalkanes, which
are important for improving the cold properties of fuel.
In summary, the results show that low temperature (product A,
temperature of 180 °C) and pressure (product E, pressure of 10 bar H2)
conditions were not sufficient for complete hydrogenation and deox-
ygenation of CNSL. On the other hand, cracking reactions of CNSL
constituents occurred to a significant extent to form linear alkanes.
Higher degrees of deoxygenation and hydrogenation were observed at
high H2 pressures (30–40 bar, reactions F and G, Table 3). A consequent
decrease in the degree of cracking of CNSL was also observed.
3.3.3. Evaluation of the effect of reaction parameters on conversion and the
deoxygenation degree
The influences of reaction parameters, such as temperature (180,
250 and 300 °C), time (5 and 10 h) and pressure (10, 20, 30 and 40 bar),
on conversion and the degree of deoxygenation are presented in Fig. 8.
Considering cardanol as the main constituent of CNSL, the conversion
of the feedstock can be estimated according to the remaining content of
cardanol (%) after the reaction, based on GC-MS analysis. The degree of
deoxygenation was also measured by GC-MS analysis according to the

Fig. 7. Effect of reaction parameters on the composition of the products obtained from the cracking hydrogenation and deoxygenation of CNSL: a) temperature
(under the conditions of 10 and 20 bar H2) and b) pressure (under the conditions of 10 and 300 °C).

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C.A. Scaldaferri and V.M.D. Pasa Renewable and Sustainable Energy Reviews 111 (2019) 303–313

Product yield (wt%)

76, 54
94, 26
98
55
60

88
HDO (wt%)

100, 26
74, 55
87–98
85–98

100
92

90

91
95
96

95

34
Present study
Reference

[47]
[41]
[48]
[49]
[42]
[45]
[46]
[50]

[51]
[52]
[53]
SV (h-1)

2
Fig. 8. Relative conversion ■ (%) and degree of deoxygenation (%) of CNSL

Pressure (bar)

100 and 200

as a function of temperature, pressure and reaction time.

content of oxygenated compounds in the products.

200
40

50
80
30
10

50

14
30
6
The results presented in Fig. 8 show that there was an increase in
CNSL conversion and in the degree of deoxygenation with increasing

Temperature (°C)

250 and 350 °C

Summary of operating conditions for hydroprocessing of bio-oils, vegetable oils and model compounds using noble metals as catalysts.
pressure. This tendency was less prominent for temperature, as the

100 and 300

deoxygenation, hydrogenation and cracking reactions occurred si-
multaneously in the range of 250–300 °C. Reaction times of 5 and 10 h

250 °C
300
350

380
300

330

300
350
200
led to similar conversions of 85% and 86%, respectively. However, the
degree of deoxygenation was higher for the 10 h reaction (77%) than
Reactor dimension (volume)

for the 5 h reaction (72%).

Among the parameters evaluated in Fig. 8, the hydrogen pressure
was the most relevant factor for reaching high conversion and deox-
ygenation. A maximum conversion of 98% and 92% deoxygenation
were obtained when 40 bar H2 was used. This is an interesting result in
view of the significant decrease in aromatic compounds, which are
100 mL
100 mL
100 mL
300 mL

100 mL

100 mL
40 mL
40 mL

undesirable in large amounts in diesel formulations. The large quantity

4 mL

of cycloalkanes (79%, as shown in Table 3) is important for the cold

properties, as previously mentioned.
Stainless steel batch

Interestingly, the greatest concentration of saturated hydrocarbons

Batch autoclave
Batch autoclave

Batch autoclave

Batch autoclave

Batch autoclave

(89%) was observed with a low content of oxygenated compounds

Reactor type

Trickle-bed

Trickle-bed

Semi Batch

(6%), aromatic compounds (3%) and phenols (2%) in the product of

Autoclave

reaction G (Table 3). A total of 98% conversion and 92% deoxygenation

were obtained at 300 °C under 40 bar H2 for 10 h in the presence of 10%
w/w catalyst.
Pd/C, Pt/C, Ru/C, Ru/Al2O3 and Ru/TiO2

This study indicates that it is possible to obtain a product analogous

to diesel oil from CNSL without the presence of oxygenated compounds
and phenols after a refining step. The total conversion of CNSL into
Pd/ZrO2, Rh/ZrO2 and Pt/ZrO2

biohydrocarbons can also be achieved using a higher H2 pressure, a

higher amount of catalyst or a different type of reactor or configuration.
It should be noted that pressures as high as 40 bar H2 are considered
Pd/Al2O3, Pt/Al2O3

low and are considered to be mild reaction conditions since the oil
Co/Al2O, Ni/Al2O3
Pd/C and H3PO4

industry uses 150–200 bar H2 in refining and petroleum upgrading

Pt/SAPO 11

processes [9,12,35].
Pd/HZSM-5
Pd/Al2O3

It should be emphasized that this study is unique considering the

Catalyst

Ru/C
Pd/C

Pd/C

Pd/C

CNSL-Pd/C catalyst system and the green diesel production approach

used, which is based on biohydrocarbons including mainly cycloalk-
anes. Few studies have been published on the use of CNSL in the field of
Phenol and phenolic monomers

biofuels. The direct use of CNSL as a fuel is unsuitable due to its high
viscosity, which causes problems, such as incomplete combustion and
low thermal efficiency. Kasiraman et al. evaluated the performance,
emission and combustion of CNSL in blends with camphor oil in diesel
Fast pyrolysis oil
Beech wood oil

Fatty acids

engines [36]. Vedharaj et al. reported the thermal cracking of CNSL and
Palm oil
Macauba oil
Soybean oil

Fatty acids

the use of the product (TC-CNSL) in different blends with diesel oil
Esters
Feedstock

Guaiacol

Palm oil
Table 4

[37].
CNSL

The pyrolysis of CNSL to produce bio-oil was reported by Das and

309
C.A. Scaldaferri and V.M.D. Pasa
Ganesh [17]. The best result was obtained with pyrolysis at 500 °C to
give a 42% liquid yield containing 20% coal and 14% gas. The most
recent study on the use of CNSL as a biofuel was published by Chat-
terjee et al. [38]. The study reported a process for CNSL decarboxyla-
tion to cardanol using a silver carbonate catalyst under 2.5 bar N2 at a
temperature range of 140–150 °C that yielded aromatic nonoxygenated
compounds. B5 and B10 blends with diesel oil and properties such as
density, viscosity, flash point, and cetane number were evaluated. The
measured properties were similar to those of fossil diesel oil; however,
further experimental investigation is required to evaluate the combus-
tion performance and emission parameters of this fuel and its blends.
Regarding upgrading reactions and their wide applicability to dif-
ferent raw materials, such as bio-oils, vegetable oils and model com-
pounds, Table 4 summarizes the operating conditions and results ob-
tained for hydroprocessing. The results are compared with the best
reaction performed in this present study.
Generally, bio-oils can be produced by fast pyrolysis of lig-
nocellulosic biomass and further upgraded to renewable fuels through
hydroprocessing. As a result of the direct pyrolysis of biomass, solids
and gases are obtained, as well as bio-oil. Bio-oil composition corre-
sponds to a complex mixture including aromatic and mainly oxyge-
nated compounds (aldehydes, ketones, acids, esters, alcohols, furans
and phenols), the latter being undesirable in drop-in fuels [39]. To
obtain hydrocarbons that can replace petrol fuels, one approach com-
monly proposed is the upgrading of bio-oil by hydrodeoxygenation and
hydrocracking [39,40].
In a recent review, Patel and Kumar reported the upgrading of bio-
oil from lignocellulosic biomass by hydroprocessing and noted im-
portant aspects, such as the operating parameters, type of catalyst and
economic analysis [39]. Wildschut et al. compared the performance of
several noble metal catalysts in the hydroprocessing of beech wood oil
(Table 4). Pd/C, followed by Ru/C, led to a higher oil yield and lower
oxygen content than Pt/C and Ru supported on alumina and titanium
oxide [41]. Another proposed alternative to reduce the oxygen content
of pyrolysis oil is fast catalytic pyrolysis, which involves the in situ
catalytic treatment of bio-oil vapor [39,40].
Commercial drop-in biofuel processes are currently centered on the
use of lipid raw materials as vegetable oils [23]. Herskowitz et al.
studied Pt supported on SAPO 11 mesoporous catalyst for production of
green diesel from soybean oil [42] (Table 4). From a one-step process a
product yield of 88% and a rate of hydrodeoxygenation (HDO) of 91%
Fig. 9. Proposed reaction pathways for the conversion of CNSL over Pd/C catalyst.
310
Renewable and Sustainable Energy Reviews 111 (2019) 303–313
were obtained. Boyas et al. investigated the hydrotreatment of rapeseed
oil with Pt/zeolite and NiMO/Al2O3 catalysts [43]. Conventional hy-
droprocessing catalysts used in refineries, composed of NiMO/Al2O3,
led to a larger yield of diesel oil than Pt on zeolites. Moreover, the use of
zeolites requires more severe reaction conditions, which implies a
higher cost of green diesel production. However, zeolites favor the
production of isoparaffins and therefore improve the chemical proper-
ties of green diesel. CoMo/Al2O3 catalyst has also presented excellent
performance in producing green diesel through deoxygenation of pal-
mitic acid, according to Boonyasuwat & Tscheikuma [44]. Silva et al.
[45] and Sousa et al. [46] reported green diesel and bio-jet fuel pro-
duction from macauba and palm oil, respectively, using mild conditions
over Pd/C. Biofuel yields higher than 85% were obtained in both stu-
dies using 10 bar H2 and 300 °C. In this case, low pressures of H2 were
enough to obtain a high deoxygenation degree of vegetable oils. In the
present study, a higher hydrogen pressure was required since CNSL is
composed of phenolic compounds.
As clearly shown in section 3.3, the present study is completely
innovative, uses mild experimental conditions, and achieves high hy-
drodeoxygenation efficiency as well as a high product yield from a new
feedstock in the hydrotreatment field.
3.4. Pathways for CNSL deoxygenation reactions
Deoxygenation reactions of phenolic compounds using catalysts
based on noble metals are well studied in the area of biomass conver-
sion, as in the deoxygenation of bio-oil or its model compounds. Fig. 9
shows the possible deoxygenation pathways based on the literature,
depending on the support type used to disperse the metal [54–57].
The first route (1) consists of direct phenol deoxygenation from the
direct breaking of the Csp2-O bond, forming benzene without the for-
mation of oxygenated compounds as intermediates. The aromatic
compound formed is subsequently hydrogenated, yielding a saturated
cycloalkane. Generally, this route is predominant for metals with high
oxophilic characteristics, such as ruthenium [55–57].
The second and third routes are based on the tautomerization of the
phenol, leading to a 2,4-cyclohexadienone intermediate, followed by
the hydrogenation of the C]O (route 2) or C]C (route 3) bond. In the
second route, hydrogenation of the C]O bond of the intermediate
occurs, leading to the formation of an unsaturated alcohol, 2,4-cyclo-
hexadienol, which is converted into benzene via the dehydration
C.A. Scaldaferri and V.M.D. Pasa
reaction. In this case, acid catalysts are required to catalyze the dehy-
dration reaction; therefore, this reaction pathway is unlikely to occur
since activated carbon supports do not exhibit measurable acidity
[55–57].
The last pathway (route 3) involves C]C bond hydrogenation of the
2,4-cyclohexadienone intermediate, yielding a second 2-cyclohexen-1-
one intermediate, which can be hydrogenated to cyclohexanone and
then to cyclohexanol. Generally, sufficiently acidic catalysts are re-
quired to catalyze the dehydration reaction from cyclohexanol to cy-
clohexene [55–57], yielding cyclohexane via the hydrogenation of cy-
clohexene on the metal sites. In the present study, one possibility for
obtaining cyclohexane is direct hydrogenolysis of the alcohol (breaking
the C-O bond) [57–60]. The presence of 3-pentadecylcyclohex-1-one in
the products suggests that the third route is the most likely pathway,
considering the properties of the Pd/C catalyst, which exhibits high
hydrogenation activity.
A study on Pd/C catalyst deactivation was published by Souza et al.,
who evaluated the stability of Pd/C and demonstrated the possibility of
reusing Pd/C after treatment to remove coke formed during the deox-
ygenation reaction of palm oil and the metal-reduction step [46]. It is
believed that the results are valid for the present study.
3.5. Cashew as a sustainable biorefinery feedstock
The results obtained in the present study expand the cashew bior-
efinery platform with the introduction of a drop-in biofuel: green diesel
from CNSL. Anacardium occidentale, the cashew tree, is cultivated
mainly for its fruit (cashew nut) and pseudo fruit (cashew apple)
commercialization; however, as many different products are made from
this plant, the cashew tree may generates a sustainable biorefinery
platform, as shown in Fig. 10.
Cashew products have a wide range of applications for different
markets, such as food, polymers, chemicals, nanotechnology, energy,
charcoal and biofuel. The pseudo fruit (cashew apple) is used in the
juice and candy industries. Cashew bagasse (cashew pomace and
cashew apple waste) is the residue from the separation of the nut from
the pseudo fruit and is used to feed livestock [61]. The nuts have large
amounts of fat, protein, carbohydrates, vitamins and minerals and are
used as food.
CNSL is obtained as a residual liquid in the roasting process of
cashew nuts and has been used as a feedstock for producing different
Fig. 10. Illustrative flowchart of biomass to value products in a potential cashew biorefinery.
311
Renewable and Sustainable Energy Reviews 111 (2019) 303–313
polymers, such as phenolic resins, epoxy, polyurethane, varnishes and
anticorrosive coatings [61,62]. Flame retardants, antioxidants, insect
repellents, antifungal substances, pesticides targeting termites in
timber, and surfactants can also be produced [62]. CNSL has also been
used as feedstock for nanodevices and nanoadditives used in the fuel
industry as antioxidants [16,61]. Cardanol-based porphyrins have been
synthesized and used in the preparation of a superparamagnetic fluor-
escence nanosystem composite material [63]. Cardanol and cholesterol
have been used to produce green nanocarriers [64]. Nanocomposites
with graphenes and epoxy from CNSL have been used to produce shape
memory polymers, as reported by Kasemsiri et al. [65]. Applications in
nanotechnology are a promising tool to improve the economic feasi-
bility of biorefinery platforms, as stated by Nizami and Rehan [66].
CNSL biofuels can be very promising for the fuel market in terms of
economic and environmental aspects. As CNSL is a residue and is oc-
casionally considered an environmental problem in the cashew in-
dustry, it has a lower price, approximately 0.15–0.25 USD/kg [16],
than soybean oil (0.91 USD/kg) and palm oil (0.82 USD/kg) [67],
which have been used as feedstocks for drop-in biofuels via HEFA
(hydroprocessing of ester and fatty acids) technology. The HEFA route
is similar to the process developed in the present paper because deox-
ygenation, hydrogenation and cracking reactions occur, although both
the feedstock and products are chemically different. Lipids and CNSL
have different prices; however, the conversion reactions may have si-
milar costs. Parajuli et al. [68] stated that in biorefineries, approxi-
mately 40–60% of the total operational costs are from the feedstock; as
a consequence, green diesel from CNSL is more economically feasible
than green diesel from renewable triglycerides and has promising
economic sustainability.
Another important aspect concerning this new conversion route is
that CNSL is an inedible oil [16,62,69]; thus, there is no food compe-
tition for this new biofuel, improving the social sustainability of this
product. The sustainability of this new fuel is influenced by important
environmental gains. As CNSL is an industrial residue, its greenhouse
emissions are lower than those from planted oleaginous cultures that
are used as feedstocks for the HEFA route. Thus, no extra changes in the
land-use patterns and no impact on water quality are present [61].
Importantly, cashew is a perennial crop, can survive for 50–60 years
[61], protects against soil erosion, can retain considerable amounts of
nutrient elements and water, and is more appropriate than annual
cultures. This perennial crop is also more resistant to pests and can
C.A. Scaldaferri and V.M.D. Pasa
produce biomass with more carbon storage, as discussed by Figueiredo
et al. [69]. These authors presented an environmental evaluation of the
cashew industry, including an LCA (life cycle assessment).
Appropriate policies to encourage production based on cashew
cultivation and the development of technologies for harnessing CNSL
should be implemented. It is strongly advisable to invest in pilot con-
tinuous-flow reactor plants for fuel synthesis based on the findings in
this study and to invest in biorefinery platform development. The data
generated in pilot units will be used to perform a more complete LCA
assessment, including the new green diesel developed in the present
study. This tool is important to evaluate the sustainability of cashew
biorefineries, as recommended by Rosen [70] and Christiansen et al.
[71].
Current efforts will improve local economies, adding value in the
cashew production chain. The main countries with large cashew pro-
duction are Vietnam, Indonesia, Nigeria, Thailand, India, Mozambique,
Tanzania, Kenya and Brazil [42]. These polices will increase the
number of employed workers in rural areas of these countries and
confer social benefits.
The world production of CNSL is approximately 1.000.000 l/year
[61]. This volume is insufficient to impact the overall fuel market;
however, there is the potential to increase production in more than 30
countries that have planted this crop [16,61,62]. CNSL production can
be considered a strategic alternative for local economies aiming to
achieve energetic self-sustainability, especially in the regions that
produce this crop. Energetic self-sustainability is especially important
during petroleum crises, in which oil prices reach high values.
3.6. Practical implications of this study
In summary, the results obtained in the current research indicate
that the evaluated reaction parameters play an important function in
the conversion of CNSL. Hydrogen pressures greater than 40 bar and
temperatures between 250 °C and 350 °C are required to obtain a high
degree of hydrogenation and deoxygenation.
Catalysts have a significant role in the selectivity and yield of pro-
ducts and make up a considerable portion of the production costs.
Among the various types of catalyst supports, active carbon has been
shown to be a promising alternative for hydroprocessing catalysts due
to its high surface area, microporosity, and hydrophobic nature in
comparison to materials such as alumina [72]. Moreover, this support
can be manufactured from residual lignocellulosic biomass [73]. In this
context, the chosen catalyst (Pd/C) has great potential to be produced
from cashew wood; such a process could be integrated into a bior-
efinery platform (Fig. 10) with environmental advantages and low cost.
More studies are also needed to optimize the operating conditions,
mainly when using continuous-flow reactors, when applying this work
on a pilot and industrial scale. For this purpose, more research is re-
quired to determine the appropriate design for a suitable pilot plant and
optimize the parameters, including hydrogen consumption, CNSL input,
process time and process temperature, to improve the economic aspects
of biofuel production. Economic feasibility studies, including the costs
of the feedstock and investments in hydrotreating units, can also be
performed and are essential to developing industrial units.
With pilot plant tests, larger volumes of this biofuel and blends
(CNSL green diesel and fossil diesel) can be produced to be used for
performance tests. Biofuel performance in engines evaluating potency,
combustion, and emissions can be measured. The physical-chemical
characteristics and chemical properties of blends with different bio-
hydrocarbon contents should be evaluated to assess the new biofuel
quality and to confirm its potential applications.
4. Concluding remarks and future prospects
A new green diesel consisting of a mixture of C15 to C21 biohy-
drocarbons, was obtained from CNSL upgrading reactions catalyzed by
312
Renewable and Sustainable Energy Reviews 111 (2019) 303–313
Pd/C under mild H2 pressure (40 bar maximum) at 300 °C. An ap-
proximately 98% yield of hydrocarbons was achieved from the con-
version of CNSL phenolic compounds to components of interest in drop-
in fuels, such as cycloalkanes and alkanes. Cycloalkanes reduce the
freezing point of the biofuel, which is relevant. This route produces
green diesel from a residual, nonedible and low-cost feedstock in a
process with a single reaction stage. This nonoxygenated biofuel is
considered to be a premium diesel and can be used with fossil diesel
blends in high concentrations without engine and infrastructure mod-
ifications. The biofuels can also be used at a low content in jet fuel
blends, contributing to reducing the environmental impact of the
aviation sector, which is currently considered one of the main chal-
lenges in the biofuel field. As Anacardium occidentale is cultivated in
different tropical and subtropical countries, this technology can be used
worldwide as a source of renewable and sustainable energy, especially
for the transportation sector.
CNSL green diesel can be integrated into the cashew biorefinery
platform, which will have a positive impact on the biobased economy
through biofuel production and value-added products, such as nano-
materials and polymers. Overall, technoeconomic assessment and life
cycle assessment are important studies to be performed as the next step
to confirm the relevance of this approach as a sustainable technology,
as highlighted in the present study.
Acknowledgements
The authors acknowledge the financial support of the Conselho
Nacional de Desenvolvimento Científico e Tecnológico - CNPq - Brazil
(project 870146/1997-1 and process 141338/2015-6).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.rser.2019.04.057.
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