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 industry in 2017. The green coconut shell represents about 80% of
the fruit's mass, and therefore approximately 2.4 million tons of
The decrease in fossil fuel reserves, climate change and the coconut shells were generated only in Brazil in 2017. This waste is
growing advance in energy demand in large urban centers are in- discarded in urban environments, beaches, landfills or dumps,
centives to seek alternative renewable sources which minimize causing great environmental impact due to the high volumes of
environmental impacts [1]. The use of lignocellulosic biomass in waste generated, in addition to its slow degradation which con-
the production of fuels and chemicals has attracted worldwide tributes to soil and water contamination. In a recent study, Nunes
interest, as it is considered a neutral carbon source which con- et al. [4] states that the proper destination of residues from pro-
tributes to reducing CO2 emissions into the atmosphere [2,3]. ducing green coconuts in a microregion of Brazil could reduce the
In this context, Cocos nucífera Linn. should be highlighted due to CH4 emission in a range of 10.2e20.9 t. It is estimated that
its high production worldwide. Brazil registered a production of 3 6.0e12.3 kg of CH4 are generated for each ton of coconut shells [4].
million tons of green coconut which were destined for the food 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
* Corresponding author. Escola Agrícola de Jundiaí- UFRN, RN 160 - Km 03,
and can be 25 times more impactful in the atmosphere than CO2
Distrito de Jundiaí, Macaíba, RN, 59280-000, Brazil.
E-mail address: renata.braga@ufrn.br (R.M. Braga).
[5].
1
These authors contributed equally. 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. Renewable Energy 191 (2022) 439e446

and there are few alternatives in some economic sectors such as The Higher Heating Value (HHV) was determined using a calo-
activated carbon, bio-adsorbent and bioethanol [6e8]. Its applica- rimeter bomb according to ASTM E711-87 [24]. The ultimate
tion in a pyrolysis process for conversion to biofuels or renewable analysis of biomass was determined using a Series IICHNS/O Per-
chemicals is an alternative for waste recovery combined with kinElmer 2400 analyzer, while the oxygen content was obtained by
environmental protection. Fast pyrolysis has stood out over the difference according to Equation (2).
years among the biomass convention processes as a thermo-
chemical conversion process of biomass into energy which gener- %O ¼ 100 - (%C þ %H þ %N) (2)
ates bio-oil in greater proportion. Bio-oil is a liquid product of
complex composition containing different classes of valuable The cellulose and hemicellulose content were determined
oxygenated organic compounds. The composition and yield of py- through acid detergent fiber (ADF) and neutral detergent fiber
rolysis products depend on the type of biomass used and the (NDF) tests following the methodology proposed by Van Soest and
conditions applied in the process [9]. The produced oxygenated Wine (1967). The Klason method was directly applied in order to
compounds can be converted into aromatic compounds of renew- determine the lignin content. Thermal analysis of the biomass was
able origin from deoxygenation reactions which take place on the performed using a thermogravimetric balance Q600 SDT from TA
surface and interior of the catalyst pores to selectively obtain a Instruments® at 30e900
C, heating rate of 5
C.min1, synthetic
better quality bio-oil [10]. air and N2 flow of 100 mL.min1 using 10 mg of biomass. The
The most widely used catalysts for improving pyrolysis products chemical composition of the biomass ash was determined by en-
are ZSM-5 zeolites, and their efficiency in cracking and deoxyge- ergy dispersive X-ray fluorescence on an EDX-720 Shimadzu
nating primary pyrolysis products from different biomasses has equipment.
been mentioned by several authors [11e13]; however, most studies
use high-cost commercial catalysts. Few reports involve low-cost 2.2. Catalyst synthesis and characterization
precursors materials such as magadiite, kaolin, rectorite, rice husk
ash, or diatomite [11,14e16] as alternative sources of Si and Al in the The catalysts were synthesized by the hydrothermal method
synthesis and application of zeolites for deoxygenating bio-oil. following the molar ratio of 10.6 TPABr: 14.3 NaOH: 2.0 Al2O3: 100
Another material rich in Si and Al is the residue from granite pro- SiO2: 2000 H2O. The alternative sources of Si and Al were: Rice
duction and processing. Granite is a magmatic rock produced on a Husk Ash (RHA 97% of SiO2 e Fig. S4 Supporting Information),
large scale in Brazil, with about 4.2 million tons of granite being diatomite residue (D: 86% of SiO2, 10% of Al2O3 and 1.4% of Fe2O3 e
produced in 2019. According to Savadkoohi et al. [17], about 50% of Fig. S2 Supporting Information) and granite processing residue (G:
the extraction and processing of granite corresponds to dry waste 54% of SiO2, 13.5% of Al2O3, 18% of Fe2O3, 12% of K2O and 1.6% of CaO
generation [17]. This waste has no consolidated destination and is e Fig. S3 Supporting Information). The DRHA-ZSM-5 (88.1% of SiO2,
accumulated in the environment, generating great environmental 4.6% of Al2O3 and 3.0% of Fe2O3 e Fig. S6 Supporting Information)
impact [17,18]. Granite waste is also potentially toxic to workers in and GRHA-ZSM-5 (84% of SiO2, 6.0% of Al2O3 and 7.7% of Fe2O3 e
mining and industry mines and can cause respiratory diseases such Fig. S7 e Supporting Information) were synthesized using rice husk
as silicosis [19]. It is notable that this residue can be reusable, and ash (RHA), diatomite residue (D) and granite residue (G) as Si and Al
therefore its use for synthesizing low-cost catalysts is a viable sources. The RHA and Al2O3 were used as complementary sources
alternative. The use of residues for producing low-cost catalysts has of Si and Al as necessary. A conventional ZSM-5 catalyst was syn-
gained prominence, however it is still necessary to optimize the thesized using NaOH, SiO2 and Al2O3 commercial (P.A. Sigma
synthesis with studies related to the mechanisms of the catalyst's Aldrich reagents) for comparison. The catalysts were subjected to
performance and product formation. heat treatment to eliminate the organic template and ion exchange
Based on this premise, the present study aims to produce to obtain HZSM-5 following the methodology presented by Barbosa
renewable aromatics through catalytic flash pyrolysis of residual et al. [11].
coconut fiber using low cost HZSM-5 catalysts synthesize with Thermogravimetric analyzes (TG) of the catalysts were carried
granite powder, diatomite waste and rice husk ash as alternative out to define their calcination temperature and identify the mass
sources of silica and aluminum. This study is concerned with green loss. These measurements were performed on a TA Instruments
chemistry principles in evaluating residues in renewable energy SDT Q600 scale from room temperature to 900
C at 10
C.min1
conversion processes in cyclical economy systems. under 50 mL.min1 of N2 using approximately 10 mg of the sample.
The crystalline phases of the zeolites were identified by X-ray
2. Experimental 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,
2.1. Biomass 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
The byproduct mesocarp of coconut (Cocos nucifera Linn.), methods, respectively. The samples were degassed at 200
C for 2 h
commonly known as coconut fiber (CF), was collected from a co- and then analyzed on a Nova 2000 device from Quanta Chrome
conut water production industry located in Extremoz-RN, Brazil. Instruments.
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 2.3. Catalytic flash pyrolysis (Py-GC/MS)
being selected. Biomass was characterized to evaluate its energy
potential through bulk density, being performed in triplicate ac- The pyrolysis was performed at 500
C, 10
C.ms1, in a Py-5200
cording to ASTM E873-82 [20]. The proximate analysis was devel- HP-R pyrolyzer from CDS Analytical coupled to a gas chromato-
oped in triplicate according to ASTM E871-82 [21], ASTM E872-85 graph using 1 mg of biomass placed between the top and bottom of
[22], and ASTM E1755-01 [23] to determine the moisture (M), quartz wool in a quartz tube (25.38 mm  1.75 mm ID) (Fig. S1-
volatile matter (VM) and ash (A) content, respectively. The fixed Supporting Information). The pyrolysis vapors were carried at
carbon content was quantified by Equation (1). 50 mL.min1 of N2 (99.999%) into a Tenax trap at room temperature
and desorption with increased temperature until 300
C, trans-
%Fixed Carbon ¼ 100 e (%Mþ%VMþ%A) (1) ferred through a transfer line heated at 300
C and injected at split
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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 such as K, Na, Ca and Mg [29]. This reveals that our results are in line
information). The products were separated by a ZB-5ms column with what is described in the literature.
(60 m  0.25 mm x 0.25 mm) using 1 mL.min1 of He (99.999%) as The results of the thermogravimetric analysis of CF show four
the carrier gas. The column oven temperature program was as main mass loss events (Fig. 1). The first event occurs between 30
follows: constant temperature of 40
C for 4 min, 40e280
C at and 180
C and is related to moisture loss. The second corresponds
10
C.min1, 280
C constant for 14.5 min. The identification of the to the decomposition of the hemicellulose structure between 190
chromatographic peaks was performed by spectral similarity and 280
C, while the third corresponds to the decomposition of
greater than 85% after a detailed analysis of each spectrum using cellulose between 290 and 385
C. The fourth, and main event,
the NIST commercial library. The catalytic pyrolysis of the CF corresponds to lignin and occurs in a wide temperature range
biomass was carried out by transferring the pyrolysis vapors to a gradually overlapping the other events, being more apparent above
catalytic bed containing 10 mg of the catalyst heated to 500
C, the 400
C. The events between 150 and 400
C basically occurred in an
products were directed to a Tenax trap and then injected into the overlapping way and indicate that the CF pyrolysis occurs through
GC/MS 3900 VARIAN under the same conditions as conventional parallel reactions. Furthermore, there is an intersecting region of
pyrolysis. MS detection was carried out under electron ionization the decomposition of hemicellulose-cellulose-lignin, and these
(EI) of 70 eV and m/z range of 40e500. Peak identification was done components can be described in literature as pseudo-components
by searching the NIST mass spectra library considered identified at [3]. This is because lignin has a polyaromatic structure concen-
a similarity above 85%. A semi-quantitative analysis was then per- trated in the spaces between the microfibrils and amorphous cel-
formed based on the ratio of peak area and biomass mass used in lulose regions, forming an associated system of polymers which is
the Pyrolysis (Area/mg of biomass). more stable when compared to cellulose and hemicellulose due to
the C¼C bonds which present greater formation energy when
3. Results and discussion compared to CO and CeOH present in carbohydrates. Finally, it is
still possible to observe an event between 750 and 860
C corre-
3.1. Biomass characterization 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- 3.2. Catalyst characterization
rolysis. The ash content, volatile content and fixed carbon are also
important in the biomass characterization, considering that these The thermogravimetric analyzes performed on non-calcined
properties are directly linked to the yield and quality of products catalysts aimed to determine the lowest possible calcination tem-
generated by the biomass pyrolysis. perature. It was agreed to use the same calcination temperature for
The inorganic part of the biomass corresponds to ashes which all catalysts for the purposes of later comparison between them in
are minerals absorbed by the plant during its growth and vary both sodium and acid forms. Successive mass losses were observed
depending on the harvest period, location and soil composition. It is in Fig. 2 for all catalysts. These events occur in a progressive way up
known that the inorganic composition of biomass act as catalyst to 550
C where minor mass losses were observed, and therefore
during pyrolysis reactions, influencing the process reactivity and this temperature was chosen to calcine the catalysts. Similar mass
the yield of the generated products [27,28]. The EDX analysis for the loss events were observed for the catalysts ZSM-5 and GRHA-ZSM-
chemical composition of CF ash showed a high content of K2O (59%) 5. The first event occurs progressively up to 200
C, which concerns
and other elements such as 14% Fe2O3, 10% CaO, 8% SiO2, 3.4% SO3 the desorption of water not linked to the zeolite structure. The
and 2.3% of P2O5. The catalytic action mechanism of biomass ashes second event occurs between 350 and 450
C and represents the
reveals that alkaline and alkaline earth metals are complexed with degradation of TPABr weakly bound to the zeolite structure. The
hydroxyl and/or phenolic groups present in the macromolecular third represents the total decomposition of the TPABr organic
biomass structure [29,30]. The complexation of these cations in the template which goes up to 510
C, and the last event more evident
cellulose structure promotes scission in the polymeric chain and for ZSM-5 occurring above 600e650
C refers to the degradation of
generates smaller compounds such as hydroxyacetaldehyde, formic residual amine coke from the organic template [34]. The DRHA-
acid, furaldehyde, among others [31,32]. In their studies, Mahade- ZSM-5 showed a different thermogravimetric curve with two
van et al. [29] showed an increase in the concentration of this type mass loss events, the first one between 150 and 250
C related to
of compounds from the increase in the concentration of metals

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.

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J.E.B. Costa, A.S. Barbosa, M.A.F. Melo et al. 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].
Fig. 2. TG/DTG curves of non-calcined ZSM-5, GRHA-ZSM-5 and DRHA-ZSM-5. 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
water desorption. The second and main mass loss event was
follows: GRHA-HZSM-5 < HZSM-5 < DRHA-HZSM-5, in the same
observed 350e470
C was associated with the degradation of
order that crystallinity increased. In contrast, the crystallite size as
TPABr.
determined by the Scherrer Equation showed a different trend from
Fig. 3 shows the FTIR spectra of the catalysts before calcination,
the other parameters: HZSM-5 < DRHA-HZSM-5 < GRHA-HZSM-5.
after ion exchange and subsequent final calcination to obtain the
The pore diameter varied between 4.1 nm and 5 nm, confirming
acid phase. A broad and low intensity band is observed at
that the catalysts studied herein are classified as mesoporous ma-
3490 cm1, being attributed to the stretching of the eOH bond of
terials. The presented textural parameters show that the alterna-
water molecules presents on the surface of the catalysts, with the
tives sources of Si and Al can be use in the HZSM-5 synthesis
exception of the granite-based catalyst that did not show signifi-
obtaining higher SBET and crystallinity than conventional HZSM-5.
cant intensity. There is a band in 1475 cm1 that represents the
stretching and deformation modes of the NeH bond of NHþ 4 ions
3.3. Catalytic flash pyrolysis (Py-GC/MS)
remaining from the ion exchange carried out to obtain the acid
form of the catalysts. This band is more evident for the diatomite-
The composition and distribution of CF pyrolysis products are
based catalyst. The spectra region between 1300 and 400 cm1
directly related to the elemental composition of the biomass used
represents the zone of effective identification of zeolites of the type
(48.8% O; 45.3% C; 5.5% H and 0.44% N). Table 3 shows the distri-
ZSM-5. At 1200 cm1 can be observed the band that represents
bution of products generated from the CF biomass pyrolysis (see
asymmetric elongation external to the TO4 group of the tetrahe-
chromatogram in Fig. S8) in which a predominance of oxygenated
dron present in the structure, while at 1130 cm1, symmetrical
products is evident.
elongation of TOT siloxane groups [35,36]. It is still possible to
The cellulose, hemicellulose and lignin macromolecules which
observe bands that occur at 792, 544 and 440 cm1 that, respec-
compose CF biomass were thermally degraded at 500
C generating
tively, represent the external symmetrical stretching of the siloxane
lighter and consequently more stable compounds. Low molecular
groups, and the five ring units characteristic of the ZSM-5 structure
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
Fig. 3. FTIR spectra of non-calcined and calcined ZSM-5, GRHA-ZSM-5, DRHA-ZSM-5 concentrations such as furfural and 3,4-dimethylfuran. Furans are
and HZSM-5. mostly formed by cracking of hemicellulose molecules, their low
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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 demethoxylation and decarboxylation reactions, followed by
synthesized with alternative sources of Si and Al based on diato- aromatization in the presence of acid catalysts [25]. An interesting
mite, granite wastes and rice husk ash, where a significant reduc- example is the low concentration of phenol shown in Fig. 6 (c),
tion in the pyrolysis oxygenated product yield is observed. where it is possible to assume that the phenol from lignin in CF
It is notable that the HZSM-5, DRHA-HZSM-5 and GRHA-HZSM- underwent to isomerization, transalalkylation and condensation
5 catalysts were efficient in deoxygenating the volatiles and se- reactions on the catalysts [42], which were able to minimize phenol
lective in forming BTEX aromatics (Fig. 6 (d)). The formation of and produce mono and polycyclic aromatics compounds. Emphasis
these renewable aromatic compounds can be explained by an for DRHA-HZMS-5 that presents the most significant conversion of
aromatization mechanism of the conventional CF pyrolysis prod- phenol in others monoaromatics compounds, such as benzene,
ucts, where oxygenated compounds undergo deoxygenation via 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. Renewable Energy 191 (2022) 439e446

The performance of zeolites synthesized with alternative sour- products deoxygenation. Finally, the pyrolysis process is a prom-
ces of Si and Al has been efficient in deoxygenating the pyrolysis ising technology to extract valuable resources the FC residues using
products of CF. The low cost DRHA-HZSM-5 proved to be more the low cost catalysts proposed.
efficient in deoxygenation reaction to produce renewable aromatics
than the conventional HZSM-5 zeolite, since a great amount (1.36 x CRediT authorship contribution statement
105 Area/mg) of oxygenated compounds of low molecular weight
(C1eC4) remain between pyrolysis products of HZSM-5. Juliana E.B. Costa: Conceptualization, Data curation, Investiga-
The catalysts synthesized with alternative sources of Si and Al in tion, Writing e original draft. Andrey S. Barbosa: Data curation,
this work present a specificity of chemical composition of their Investigation, Formal analysis, Writing e original draft. Marcus A.F.
source. For example, the chemical composition of the GRHA-HZSM- Melo: Resources, Supervision, Writing e review & editing. Dulce
5 and DRHA-HZSM-5 catalysts has a significant Fe percentage of M.A. Melo: Resources, Writing e review & editing. Rodolfo L.B.A.
7.7% and 3.0%, respectively. Recent studies have shown that the Medeiros: Data curation, Writing e review & editing. Renata M.
coexistence of Al and Fe in the coordination structure of HZSM-5 Braga: Conceptualization, Resources, Project administration, Su-
can bring benefits related to acidity and morphological proper- pervision, Writing e review & editing.
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 Declaration of competing interest
authors reported that the Si/Al ratio influences an improvement in
the zeolite properties when there is Fe in its structure, with it being The authors declare that they have no known competing
ideal that this Si/Al ratio is close to 45 for maximum acidity possible financial interests or personal relationships that could have
since a greater amount of Brønsted and Lewis acidic sites is ach- appeared to influence the work reported in this paper.
ieved due to the ideal synergistic effect between Fe and Al on
zeolite. Although this evidence has already been reported in the Acknowledgements
literature and the zeolites synthesized in this work have a Si/Al
ratio of 50, to consider this effect further studies should be The authors gratefully acknowledge CNPq (307433/2020-0),
developed. CAPES, PETROBRAS (Project e Catalisadores estruturados) and
The Brønsted acid sites are of relevant importance for propa- LABTAM/NUPPRAR/UFRN for use of facilities. This study was
gation of the oxon ions, which are responsible for forming the CeC financed in part by the Coordenaça~o de Aperfeiçoamento de Pessoal
bond and thus generate hydrocarbons. Thus, oxygenated C1eC4 de Nível Superior - Brasil (CAPES) - Finance Code 001.
compounds can be deoxygenated within the zeolite pores by the
formation of the oxon ion as olefins are formed and are then Appendix A. Supplementary data
aromatized in the presence of gases [43,44]. The highest specific
area (357 m2/g) and crystallinity of DRHA-HZSM-5 made it more Supplementary data to this article can be found online at
selective for deoxygenation when compared to other catalysts. The https://doi.org/10.1016/j.renene.2022.03.111.
BTEX yield shown in Fig. 6 (d) is related to SBet area presented in
Table 2 in which values increase GRHA-HZSM-5 < HZSM- References
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