Renewable Energy 191 (2022) 439e446

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Renewable aromatics through catalytic pyrolysis of coconut fiber

(Cocos nucífera Linn.) using low cost HZSM-5
Juliana E.B. Costa a, e, 1, Andrey S. Barbosa a, 1, Marcus A.F. Melo a, c, Dulce M.A. Melo a, b,
Rodolfo L.B.A. Medeiros a, Renata M. Braga a, d, *
a
rio de Tecnologia Ambiental/NUPPRAR/Universidade Federal do Rio Grande do Norte, Natal, Brazil
Laborato
b
Universidade Federal do Rio Grande do Norte, Instituto de Química, Natal, RN, 59078-970, Brazil
c
Universidade Federal do Rio Grande do Norte, Dep. Engenharia Química, Natal, RN, 59078-970, Brazil
d
Escola Agrícola de Jundiaí/Universidade Federal do Rio Grande do Norte, Macaíba, 59280-000, Brazil
e
Universidade Federal do Rio Grande do Norte, PPGCEM, Natal, RN, 59078-970, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Renewable aromatic compounds with high commercial value were generated through catalytic pyrolysis
Received 11 November 2021 of a residual biomass using a low cost HZSM-5 catalysts. The residual coconut fiber (CF) was charac-
Received in revised form terized by bulk density, cellulose, hemicellulose and lignin content, HHV, TG/DTG in order to analyze its
24 February 2022
energy potential, and ash chemical composition by XRF. A high production of oxygenated products was
Accepted 21 March 2022
observed in the conventional coconut fiber pyrolysis Py-GC/MS at 500
C. The catalytic pyrolysis was
Available online 28 March 2022
performed using HZSM-5 catalysts synthesized using granite dust residue (G), diatomite residue (D) and
rice husk ash (RHA) as alternative sources of Si and Al. The catalysts were characterized by TG/DTG, FTIR,
Keywords:
Catalytic flash pyrolysis
specific area, XRF e XRD. The results presented in this work show that the catalysts were able to
HZSM-5 deoxygenate pyrolysis products, generating renewable aromatic compounds such as benzene, toluene,
Granite dust residue xylene, among others. The aromatic yield increased with increased specific area of catalyst which was
Rice husk ash directly influenced by its crystallite size. The highest aromatic content was found for DRHA-HZSM-5
Coconut fiber waste synthesized with D residue and RHA, confirming the best performance in the conversion of oxygen-
ates into mono and polycyclic aromatics compounds which confirms the efficiency of catalysts over
conventional HZSM-5.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction
The decrease in fossil fuel reserves, climate change and the
growing advance in energy demand in large urban centers are in-
centives to seek alternative renewable sources which minimize
environmental impacts [1]. The use of lignocellulosic biomass in
the production of fuels and chemicals has attracted worldwide
interest, as it is considered a neutral carbon source which con-
tributes to reducing CO2 emissions into the atmosphere [2,3].
In this context, Cocos nucífera Linn. should be highlighted due to
its high production worldwide. Brazil registered a production of 3
million tons of green coconut which were destined for the food
* Corresponding author. Escola Agrícola de Jundiaí- UFRN, RN 160 - Km 03,
Distrito de Jundiaí, Macaíba, RN, 59280-000, Brazil.
E-mail address: renata.braga@ufrn.br (R.M. Braga).
1
These authors contributed equally.
industry in 2017. The green coconut shell represents about 80% of
the fruit's mass, and therefore approximately 2.4 million tons of
coconut shells were generated only in Brazil in 2017. This waste is
discarded in urban environments, beaches, landfills or dumps,
causing great environmental impact due to the high volumes of
waste generated, in addition to its slow degradation which con-
tributes to soil and water contamination. In a recent study, Nunes
et al. [4] states that the proper destination of residues from pro-
ducing green coconuts in a microregion of Brazil could reduce the
CH4 emission in a range of 10.2e20.9 t. It is estimated that
6.0e12.3 kg of CH4 are generated for each ton of coconut shells [4].
Clearly, we could therefore estimate that about 14.4e29.5  104
tons of CH4 were emitted into the atmosphere if the proper desti-
nation was not performed for Brazilian green coconut production
residue in 2017. This gas is a major cause of the greenhouse effect
and can be 25 times more impactful in the atmosphere than CO2
[5].
Concern about the destination of coconut fiber waste has grown

https://doi.org/10.1016/j.renene.2022.03.111
0960-1481/© 2022 Elsevier Ltd. All rights reserved.
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al.
and there are few alternatives in some economic sectors such as
activated carbon, bio-adsorbent and bioethanol [6e8]. Its applica-
tion in a pyrolysis process for conversion to biofuels or renewable
chemicals is an alternative for waste recovery combined with
environmental protection. Fast pyrolysis has stood out over the
years among the biomass convention processes as a thermo-
chemical conversion process of biomass into energy which gener-
ates bio-oil in greater proportion. Bio-oil is a liquid product of
complex composition containing different classes of valuable
oxygenated organic compounds. The composition and yield of py-
rolysis products depend on the type of biomass used and the
conditions applied in the process [9]. The produced oxygenated
compounds can be converted into aromatic compounds of renew-
able origin from deoxygenation reactions which take place on the
surface and interior of the catalyst pores to selectively obtain a
better quality bio-oil [10].
The most widely used catalysts for improving pyrolysis products
are ZSM-5 zeolites, and their efficiency in cracking and deoxyge-
nating primary pyrolysis products from different biomasses has
been mentioned by several authors [11e13]; however, most studies
use high-cost commercial catalysts. Few reports involve low-cost
precursors materials such as magadiite, kaolin, rectorite, rice husk
ash, or diatomite [11,14e16] as alternative sources of Si and Al in the
synthesis and application of zeolites for deoxygenating bio-oil.
Another material rich in Si and Al is the residue from granite pro-
duction and processing. Granite is a magmatic rock produced on a
large scale in Brazil, with about 4.2 million tons of granite being
produced in 2019. According to Savadkoohi et al. [17], about 50% of
the extraction and processing of granite corresponds to dry waste
generation [17]. This waste has no consolidated destination and is
accumulated in the environment, generating great environmental
impact [17,18]. Granite waste is also potentially toxic to workers in
mining and industry mines and can cause respiratory diseases such
as silicosis [19]. It is notable that this residue can be reusable, and
therefore its use for synthesizing low-cost catalysts is a viable
alternative. The use of residues for producing low-cost catalysts has
gained prominence, however it is still necessary to optimize the
synthesis with studies related to the mechanisms of the catalyst's
performance and product formation.
Based on this premise, the present study aims to produce
renewable aromatics through catalytic flash pyrolysis of residual
coconut fiber using low cost HZSM-5 catalysts synthesize with
granite powder, diatomite waste and rice husk ash as alternative
sources of silica and aluminum. This study is concerned with green
chemistry principles in evaluating residues in renewable energy
conversion processes in cyclical economy systems.
2. Experimental
2.1. Biomass
The byproduct mesocarp of coconut (Cocos nucifera Linn.),
commonly known as coconut fiber (CF), was collected from a co-
conut water production industry located in Extremoz-RN, Brazil.
The obtained biomass was dried at 100
C for 12 h and ground in a
knife mill, with particle sizes from 0.074 to 0.104 mm subsequently
being selected. Biomass was characterized to evaluate its energy
potential through bulk density, being performed in triplicate ac-
cording to ASTM E873-82 [20]. The proximate analysis was devel-
oped in triplicate according to ASTM E871-82 [21], ASTM E872-85
[22], and ASTM E1755-01 [23] to determine the moisture (M),
volatile matter (VM) and ash (A) content, respectively. The fixed
carbon content was quantified by Equation (1).
%Fixed Carbon ¼ 100 e (%Mþ%VMþ%A) (1)
440
Renewable Energy 191 (2022) 439e446
The Higher Heating Value (HHV) was determined using a calo-
rimeter bomb according to ASTM E711-87 [24]. The ultimate
analysis of biomass was determined using a Series IICHNS/O Per-
kinElmer 2400 analyzer, while the oxygen content was obtained by
difference according to Equation (2).
%O ¼ 100 - (%C þ %H þ %N) (2)
The cellulose and hemicellulose content were determined
through acid detergent fiber (ADF) and neutral detergent fiber
(NDF) tests following the methodology proposed by Van Soest and
Wine (1967). The Klason method was directly applied in order to
determine the lignin content. Thermal analysis of the biomass was
performed using a thermogravimetric balance Q600 SDT from TA
Instruments® at 30e900
C, heating rate of 5
C.min1, synthetic
air and N2 flow of 100 mL.min1 using 10 mg of biomass. The
chemical composition of the biomass ash was determined by en-
ergy dispersive X-ray fluorescence on an EDX-720 Shimadzu
equipment.
2.2. Catalyst synthesis and characterization
The catalysts were synthesized by the hydrothermal method
following the molar ratio of 10.6 TPABr: 14.3 NaOH: 2.0 Al2O3: 100
SiO2: 2000 H2O. The alternative sources of Si and Al were: Rice
Husk Ash (RHA 97% of SiO2 e Fig. S4 Supporting Information),
diatomite residue (D: 86% of SiO2, 10% of Al2O3 and 1.4% of Fe2O3 e
Fig. S2 Supporting Information) and granite processing residue (G:
54% of SiO2, 13.5% of Al2O3, 18% of Fe2O3, 12% of K2O and 1.6% of CaO
e Fig. S3 Supporting Information). The DRHA-ZSM-5 (88.1% of SiO2,
4.6% of Al2O3 and 3.0% of Fe2O3 e Fig. S6 Supporting Information)
and GRHA-ZSM-5 (84% of SiO2, 6.0% of Al2O3 and 7.7% of Fe2O3 e
Fig. S7 e Supporting Information) were synthesized using rice husk
ash (RHA), diatomite residue (D) and granite residue (G) as Si and Al
sources. The RHA and Al2O3 were used as complementary sources
of Si and Al as necessary. A conventional ZSM-5 catalyst was syn-
thesized using NaOH, SiO2 and Al2O3 commercial (P.A. Sigma
Aldrich reagents) for comparison. The catalysts were subjected to
heat treatment to eliminate the organic template and ion exchange
to obtain HZSM-5 following the methodology presented by Barbosa
et al. [11].
Thermogravimetric analyzes (TG) of the catalysts were carried
out to define their calcination temperature and identify the mass
loss. These measurements were performed on a TA Instruments
SDT Q600 scale from room temperature to 900
C at 10
C.min1
under 50 mL.min1 of N2 using approximately 10 mg of the sample.
The crystalline phases of the zeolites were identified by X-ray
diffraction using a XRD-7000 Shimadzu equipment with CueK a
radiation source (k ¼ 1.5409 Å), voltage of 30 kV, current of 30 mA,
step of 0.02 and speed of 0.01/s. The specific area and pore diameter
of the calcined catalysts were calculated by the BET and BJH
methods, respectively. The samples were degassed at 200
C for 2 h
and then analyzed on a Nova 2000 device from Quanta Chrome
Instruments.
2.3. Catalytic flash pyrolysis (Py-GC/MS)
The pyrolysis was performed at 500
C, 10
C.ms1, in a Py-5200
HP-R pyrolyzer from CDS Analytical coupled to a gas chromato-
graph using 1 mg of biomass placed between the top and bottom of
quartz wool in a quartz tube (25.38 mm  1.75 mm ID) (Fig. S1-
Supporting Information). The pyrolysis vapors were carried at
50 mL.min1 of N2 (99.999%) into a Tenax trap at room temperature
and desorption with increased temperature until 300
C, trans-
ferred through a transfer line heated at 300
C and injected at split
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al. Renewable Energy 191 (2022) 439e446

mode of 1:30 in a GC-MS/MS 3900 VARIAN (Figue S1-supportin
information). The products were separated by a ZB-5ms column
(60 m  0.25 mm x 0.25 mm) using 1 mL.min1 of He (99.999%) as
the carrier gas. The column oven temperature program was as
follows: constant temperature of 40
C for 4 min, 40e280
C at
10
C.min1, 280
C constant for 14.5 min. The identification of the
chromatographic peaks was performed by spectral similarity
greater than 85% after a detailed analysis of each spectrum using
the NIST commercial library. The catalytic pyrolysis of the CF
biomass was carried out by transferring the pyrolysis vapors to a
catalytic bed containing 10 mg of the catalyst heated to 500
C, the
products were directed to a Tenax trap and then injected into the
GC/MS 3900 VARIAN under the same conditions as conventional
pyrolysis. MS detection was carried out under electron ionization
(EI) of 70 eV and m/z range of 40e500. Peak identification was done
by searching the NIST mass spectra library considered identified at
a similarity above 85%. A semi-quantitative analysis was then per-
formed based on the ratio of peak area and biomass mass used in
the Pyrolysis (Area/mg of biomass).
3. Results and discussion
3.1. Biomass characterization
such as K, Na, Ca and Mg [29]. This reveals that our results are in line
with what is described in the literature.
The results of the thermogravimetric analysis of CF show four
main mass loss events (Fig. 1). The first event occurs between 30
and 180
C and is related to moisture loss. The second corresponds
to the decomposition of the hemicellulose structure between 190
and 280
C, while the third corresponds to the decomposition of
cellulose between 290 and 385
C. The fourth, and main event,
corresponds to lignin and occurs in a wide temperature range
gradually overlapping the other events, being more apparent above
400
C. The events between 150 and 400
C basically occurred in an
overlapping way and indicate that the CF pyrolysis occurs through
parallel reactions. Furthermore, there is an intersecting region of
the decomposition of hemicellulose-cellulose-lignin, and these
components can be described in literature as pseudo-components
[3]. This is because lignin has a polyaromatic structure concen-
trated in the spaces between the microfibrils and amorphous cel-
lulose regions, forming an associated system of polymers which is
more stable when compared to cellulose and hemicellulose due to
the C¼C bonds which present greater formation energy when
compared to CO and CeOH present in carbohydrates. Finally, it is
still possible to observe an event between 750 and 860
C corre-
sponding to pyro-condensation and carbonization [33].

The characterization results (Table 1) show a high energetic

potential of coconut fiber (CF) residues for application in flash py-
rolysis. The ash content, volatile content and fixed carbon are also
important in the biomass characterization, considering that these
properties are directly linked to the yield and quality of products
generated by the biomass pyrolysis.
The inorganic part of the biomass corresponds to ashes which
are minerals absorbed by the plant during its growth and vary
depending on the harvest period, location and soil composition. It is
known that the inorganic composition of biomass act as catalyst
during pyrolysis reactions, influencing the process reactivity and
the yield of the generated products [27,28]. The EDX analysis for the
chemical composition of CF ash showed a high content of K2O (59%)
and other elements such as 14% Fe2O3, 10% CaO, 8% SiO2, 3.4% SO3
and 2.3% of P2O5. The catalytic action mechanism of biomass ashes
reveals that alkaline and alkaline earth metals are complexed with
hydroxyl and/or phenolic groups present in the macromolecular
biomass structure [29,30]. The complexation of these cations in the
cellulose structure promotes scission in the polymeric chain and
generates smaller compounds such as hydroxyacetaldehyde, formic
acid, furaldehyde, among others [31,32]. In their studies, Mahade-
van et al. [29] showed an increase in the concentration of this type
of compounds from the increase in the concentration of metals
3.2. Catalyst characterization
The thermogravimetric analyzes performed on non-calcined
catalysts aimed to determine the lowest possible calcination tem-
perature. It was agreed to use the same calcination temperature for
all catalysts for the purposes of later comparison between them in
both sodium and acid forms. Successive mass losses were observed
in Fig. 2 for all catalysts. These events occur in a progressive way up
to 550
C where minor mass losses were observed, and therefore
this temperature was chosen to calcine the catalysts. Similar mass
loss events were observed for the catalysts ZSM-5 and GRHA-ZSM-
5. The first event occurs progressively up to 200
C, which concerns
the desorption of water not linked to the zeolite structure. The
second event occurs between 350 and 450
C and represents the
degradation of TPABr weakly bound to the zeolite structure. The
third represents the total decomposition of the TPABr organic
template which goes up to 510
C, and the last event more evident
for ZSM-5 occurring above 600e650
C refers to the degradation of
residual amine coke from the organic template [34]. The DRHA-
ZSM-5 showed a different thermogravimetric curve with two
mass loss events, the first one between 150 and 250
C related to

Table 1
CF characterization in dry basis.

CF (wt. %) CS [25] CCP [26]

Proximate analysis (%)

Moisture 9.5 ± 0.15 10.27 ± 0.23 11.60
Ash 7.84 ± 0.7 4.33 ± 0.12 3.70
Volatiles 77.85 ± 1.02 73.53 ± 0.54 70.10
Fixed carbon 4.81 11.87 ± 0.38 14.60
Ultimate analysis (%)
C 45.26 ± 0.3 47.38 ± 0.23 36.20
H 5.55 ± 0.2 6.56 ± 0.07 0.92
N 0.44 ± 0.2 0.54 ± 0.02 0.36
O 48.77 45.32 ± 0.16 61.71
Cellulose (%) 28.93 27.23 ± 0.48 26.80
Hemicellulose (%) 7.05 37.49 ± 0.26 17.20
Lignin (%) 32.75 30.17 ± 0.41 30.50
HHV (MJ/kg) 19.72 16.27 ± 0.18 16.72
Bulk density (kg/m3) 232 549 ± 3.21 135
Fig. 1. TG/DTG curves of mesocarp of Cocos nucifera Linn.

441
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al.
Fig. 2. TG/DTG curves of non-calcined ZSM-5, GRHA-ZSM-5 and DRHA-ZSM-5.
water desorption. The second and main mass loss event was
observed 350e470
C was associated with the degradation of
TPABr.
Fig. 3 shows the FTIR spectra of the catalysts before calcination,
after ion exchange and subsequent final calcination to obtain the
acid phase. A broad and low intensity band is observed at
3490 cm1, being attributed to the stretching of the eOH bond of
water molecules presents on the surface of the catalysts, with the
exception of the granite-based catalyst that did not show signifi-
cant intensity. There is a band in 1475 cm1 that represents the
stretching and deformation modes of the NeH bond of NHþ 4 ions
remaining from the ion exchange carried out to obtain the acid
form of the catalysts. This band is more evident for the diatomite-
based catalyst. The spectra region between 1300 and 400 cm1
represents the zone of effective identification of zeolites of the type
ZSM-5. At 1200 cm1 can be observed the band that represents
asymmetric elongation external to the TO4 group of the tetrahe-
dron present in the structure, while at 1130 cm1, symmetrical
elongation of TOT siloxane groups [35,36]. It is still possible to
observe bands that occur at 792, 544 and 440 cm1 that, respec-
tively, represent the external symmetrical stretching of the siloxane
groups, and the five ring units characteristic of the ZSM-5 structure
Fig. 3. FTIR spectra of non-calcined and calcined ZSM-5, GRHA-ZSM-5, DRHA-ZSM-5
and HZSM-5.
442
Renewable Energy 191 (2022) 439e446
[35].
The XRD results presented in Fig. 4 show that both catalysts as
alternative sources of Si and Al (DRHA-HZSM-5 and GRHA-HZSM-
5) mainly presented a similar crystalline MFI phase to the con-
ventional HZSM-5, thus confirming the efficiency and success of
the method used in the synthesis by using alternative sources, since
the formation of crystalline phases can be proven from the XRD
analysis and refinement. In the case of zeolite, an orthorhombic
structure of zeolite (01-079-1638) was confirmed from granite with
few associated peaks as phases present in the alternative source
such as quartz (01-086-1560) and orthoclase (01-086-0437). The
crystallographic patterns shown in Fig. 4 are in accordance with
those presented by the reference zeolite indicated in the Interna-
tional Zeolites Association (IZA) database.
The textural proprieties are shown in Table 2. High specific
surface area values were obtained for all catalysts, and these results
are compatible with values found by other authors for HZSM-5 [37].
Fouad et al. [38] observed that the specific area in ZSM-5 materials
increased with increasing crystallinity [38], the same occurred with
the catalysts presented herein, where the specific area increased as
follows: GRHA-HZSM-5 < HZSM-5 < DRHA-HZSM-5, in the same
order that crystallinity increased. In contrast, the crystallite size as
determined by the Scherrer Equation showed a different trend from
the other parameters: HZSM-5 < DRHA-HZSM-5 < GRHA-HZSM-5.
The pore diameter varied between 4.1 nm and 5 nm, confirming
that the catalysts studied herein are classified as mesoporous ma-
terials. The presented textural parameters show that the alterna-
tives sources of Si and Al can be use in the HZSM-5 synthesis
obtaining higher SBET and crystallinity than conventional HZSM-5.
3.3. Catalytic flash pyrolysis (Py-GC/MS)
The composition and distribution of CF pyrolysis products are
directly related to the elemental composition of the biomass used
(48.8% O; 45.3% C; 5.5% H and 0.44% N). Table 3 shows the distri-
bution of products generated from the CF biomass pyrolysis (see
chromatogram in Fig. S8) in which a predominance of oxygenated
products is evident.
The cellulose, hemicellulose and lignin macromolecules which
compose CF biomass were thermally degraded at 500
C generating
lighter and consequently more stable compounds. Low molecular
weight compounds up to four carbons (C1eC4) which correspond to
4.8x105 of total chromatogram area per mg of biomass (Area/mg)
were identified as 2-propanone, methyl vinyl ketone, and acetic
anhydride. Light weight organic acids are well known as pyrolysis
products of lignocellulosic biomass, one of their origin mechanism
being related to the cleavage of the b-1,4-glycosidic bond of the
cellulose macromolecule which is converted into levoglucosan in-
termediate and later degraded until it formed smaller compound
molecules [39]. The biomass ash improve the C1eC4 yield, espe-
cially when it contain alkali metal composition as it act as natural
cracking catalyst [27,28]. CF is a potassium-rich biomass (59%) that
significantly influence the production of these compounds. The
absence of anhydrosugars and cellulose derivatives such as levo-
glucosan is explained by ash secondary cracking effect catalyst.
After C1eC4 phenols were the main compound class identified in
the pyrolysis products of CF. Their formation is directly related to
the degradation and demethoxylation reactions of the guaiacyl (G)
and syringyl (S) lignin macromolecule the main component
(32.75%) of CF biomass, directing the formations of phenols and
C1eC4. Compounds such as 2,6-Methoxy-4-(2-propenyl)-phenol
and 2,6-Dimethoxy-phenol can be associated with primary pyrol-
ysis products of S lignin. Other compounds were identified in low
concentrations such as furfural and 3,4-dimethylfuran. Furans are
mostly formed by cracking of hemicellulose molecules, their low
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al. Renewable Energy 191 (2022) 439e446

Fig. 4. XRD patterns of Si and Al precursors, alternatives, and conventional HZSM-5.

Table 2
Textural and Crystallinity properties of catalyst.

Sample SBET (m2/g) Pore Volume (cm3/g) Pore diameter (nm) Crystallinity (%) Crystallite Size (nm)

HZSM-5 310 0.053 5.0 92.0 38.2

GRHA-HZSM-5 300 0.020 4.4 91.4 52.9
DRHA-HZSM-5 357 0.041 4.1 93.0 45.2

Table 3
Pyrolysis products of CF at 500
C.

RTa(min) Compound (WM) m/z CAS No. Area/mg (104)

2.0e6.5 C1eC4 e 64-19-7 48.0

7.0 3,4 e Dimethylfurano (C6H8O) 96 20843-07-6 5.4
7.8 Furfural (C5H4O2) 96 498-60-2 6.0
8,0 2-Methyl-3-hexyno (C7H12) 96 36566-80-0 0.1
9.7 Cyclohexanone (C6H10O) 98 108-94-1 4.7
10.2 Phenol (C6H6O) 94 108-95-1 25.0
10.8 2-Cyclohexen-1-one (C6H8O) 96 930-68-7 1.2
11.5 2-Methylphenol (C7H8O) 108 95-48-7 12.0
12.3 2-Methoxyphenol (C7H8O2) 124 150-76-5 9.0
13.4 2-Hydroxyphenol (C6H6O2) 110 120-80-9 31.0
14.4 2-Methoxy-4-vinylphenol (C9H10O2) 159 7786-61-0 8.0
15.8 1,4-Benzenedimethanol (C8H10O2) 138 598-29-7 2.9
16.8 2,6-Dimethoxy-phenol (C8H10O3) 154 91-10-1 7.2
17.6 2-Methoxy-4-(1-propenyl)-phenol (C10H12O2) 164 97-54-1 3.6
17.9 3-Methoxycatechol (C7H8O3) 140 934-00-9 2.1
19.7 2,6-Methoxy-4-(2-propenyl)-phenol (C11H14O3) 194 6627-88-9 5.8
21.9 1-(4-Hydroxy-3,5-dimethoxyfenil)-ethanone (C10H12O4) 196 2478-38-8 1.2
a
Retention time (min).

concentration found in CF pyrolysis products are related to CF catalytic pyrolysis processes, in which their catalytic activity in the
hemicellulose content (7.05%). deoxygenation and production of aromatic compounds is quite
HZSM-5 zeolites are widely used and above all quite efficient in remarkable [12,25,40,41]. Fig. 5 shows the chromatograms of

443
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al. Renewable Energy 191 (2022) 439e446

Fig. 5. Chromatograms of catalytic flash pyrolysis of FC.

products generated from flash catalytic pyrolysis using zeolites
synthesized with alternative sources of Si and Al based on diato-
mite, granite wastes and rice husk ash, where a significant reduc-
tion in the pyrolysis oxygenated product yield is observed.
It is notable that the HZSM-5, DRHA-HZSM-5 and GRHA-HZSM-
5 catalysts were efficient in deoxygenating the volatiles and se-
lective in forming BTEX aromatics (Fig. 6 (d)). The formation of
these renewable aromatic compounds can be explained by an
aromatization mechanism of the conventional CF pyrolysis prod-
ucts, where oxygenated compounds undergo deoxygenation via
demethoxylation and decarboxylation reactions, followed by
aromatization in the presence of acid catalysts [25]. An interesting
example is the low concentration of phenol shown in Fig. 6 (c),
where it is possible to assume that the phenol from lignin in CF
underwent to isomerization, transalalkylation and condensation
reactions on the catalysts [42], which were able to minimize phenol
and produce mono and polycyclic aromatics compounds. Emphasis
for DRHA-HZMS-5 that presents the most significant conversion of
phenol in others monoaromatics compounds, such as benzene,
toluene, xylene and ethylbenzene (BETX).

Fig. 6. Pyrolysis products distribution of Cocos nucifera Linn: (a) CF conventional pyrolysis products distribution, (b) Oxygenated and non-oxygenated products distribution of FC
catalytic pyrolysis, (c) FC catalytic pyrolysis distribution and (d) BTEX products distribution of FC catalytic pyrolysis.

444
J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al.
The performance of zeolites synthesized with alternative sour-
ces of Si and Al has been efficient in deoxygenating the pyrolysis
products of CF. The low cost DRHA-HZSM-5 proved to be more
efficient in deoxygenation reaction to produce renewable aromatics
than the conventional HZSM-5 zeolite, since a great amount (1.36 x
105 Area/mg) of oxygenated compounds of low molecular weight
(C1eC4) remain between pyrolysis products of HZSM-5.
The catalysts synthesized with alternative sources of Si and Al in
this work present a specificity of chemical composition of their
source. For example, the chemical composition of the GRHA-HZSM-
5 and DRHA-HZSM-5 catalysts has a significant Fe percentage of
7.7% and 3.0%, respectively. Recent studies have shown that the
coexistence of Al and Fe in the coordination structure of HZSM-5
can bring benefits related to acidity and morphological proper-
ties. Li et al. [43] and Lee et al. [44] evaluated incorporating Fe into
the HZSM-5 structure in MTH and DTG processes [43,44]. These
authors reported that the Si/Al ratio influences an improvement in
the zeolite properties when there is Fe in its structure, with it being
ideal that this Si/Al ratio is close to 45 for maximum acidity possible
since a greater amount of Brønsted and Lewis acidic sites is ach-
ieved due to the ideal synergistic effect between Fe and Al on
zeolite. Although this evidence has already been reported in the
literature and the zeolites synthesized in this work have a Si/Al
ratio of 50, to consider this effect further studies should be
developed.
The Brønsted acid sites are of relevant importance for propa-
gation of the oxon ions, which are responsible for forming the CeC
bond and thus generate hydrocarbons. Thus, oxygenated C1eC4
compounds can be deoxygenated within the zeolite pores by the
formation of the oxon ion as olefins are formed and are then
aromatized in the presence of gases [43,44]. The highest specific
area (357 m2/g) and crystallinity of DRHA-HZSM-5 made it more
selective for deoxygenation when compared to other catalysts. The
BTEX yield shown in Fig. 6 (d) is related to SBet area presented in
Table 2 in which values increase GRHA-HZSM-5 < HZSM-
5 < DRHA-HZSM-5, highlighting the DRHA-HZSM-5 that produced
the highest PAHs amount which can be attributed to selective form.
The textural proprieties and the presence of Fe in the structure
of the GRHA-HZSM-5 and DRHA-HZSM-5 catalysts influenced
generation of renewable aromatic compounds, mainly in the diat-
omite catalyst since it has 3% iron in its composition. The results
presented in this paper show that it is possible to selectively pro-
duce aromatic compounds of renewable origin from a residual
biomass with low-cost catalysts and which have unique properties
given the original composition of their sources.
4. Conclusions
The conversion of CF into renewable aromatics of high com-
mercial value was investigated using catalytic flash pyrolysis ex-
periments. Flash pyrolysis of CF resulted in oxygenated products
such as acetic acid, phenols and furans compounds that were
converted into aromatics over the low-cost synthesized catalysts.
The HZSM-5 catalysts were successfully synthesized using RHA,
diatomite and granite dust residues as alternative sources of Si and
Al and performed the deoxygenation and aromatization of CF py-
rolysis products, generating aromatic compounds such as BTEX that
are of interest industrial. The DRHA-HZSM-5 was more selective for
deoxygenation reactions, producing higher yield of mono and
polycyclic aromatic compounds than GRHA-HZSM-5 and conven-
tional HZSM-5. This result can be related to the textural proprieties
and presence of Fe in its composition, which cause greater acidity in
this catalyst when compared with HZSM-5. The results presented
in this study confirm an eco-friendly catalyst produced by half price
of conventional one that are efficient in the lignocellulosic pyrolysis
445
Renewable Energy 191 (2022) 439e446
products deoxygenation. Finally, the pyrolysis process is a prom-
ising technology to extract valuable resources the FC residues using
the low cost catalysts proposed.
CRediT authorship contribution statement
Juliana E.B. Costa: Conceptualization, Data curation, Investiga-
tion, Writing e original draft. Andrey S. Barbosa: Data curation,
Investigation, Formal analysis, Writing e original draft. Marcus A.F.
Melo: Resources, Supervision, Writing e review & editing. Dulce
M.A. Melo: Resources, Writing e review & editing. Rodolfo L.B.A.
Medeiros: Data curation, Writing e review & editing. Renata M.
Braga: Conceptualization, Resources, Project administration, Su-
pervision, Writing e review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge CNPq (307433/2020-0),
CAPES, PETROBRAS (Project e Catalisadores estruturados) and
LABTAM/NUPPRAR/UFRN for use of facilities. This study was
financed in part by the Coordenaça~o de Aperfeiçoamento de Pessoal
de Nível Superior - Brasil (CAPES) - Finance Code 001.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.renene.2022.03.111.
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