Industrial Crops & Products xxx (xxxx) xxx–xxx

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Thermochemical conversion and characterization of cocoa pod husks a

potential agricultural waste from Ghana
⁎
Maxwell Adjin-Tetteha, N. Asiedua, , David Dodoo-Arhinb, Ayman Karamc,d,
⁎
Prince Nana Amaniampongd,
a
Department of Chemical Engineering, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
b
Department of Materials Science and Engineering, University of Ghana, Ghana
c
Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers, CNRS, ENSIP, 1 rue Marcel Doré, TSA41105, 86073 Poitiers, France
d
INCREASE (FR CNRS 3707), ENSI Poitiers, 1 rue Marcel Doré, TSA41105, 86073 Poitiers, France

A R T I C L E I N F O A B S T R A C T

Keywords: Bio-Oils derived from biomass pyrolysis are promising feedstock for the direct production of valuable platform
Biomass chemicals, fuels and energy from renewable and sustainable resources. Among the numerous technologies uti-
Pyrolysis lized for biomass pyrolysis, fast pyrolysis technologies are chosen for liquid products yield maximization, and
Cocoa pod husks characterized by short residence times for solids and vapors, operating temperatures in above ≥500 °C and very
Bio-oil
high heating rates. Inspired by the vast potential of biomass pyrolysis bio-oils, a thermochemical conversion (fast
Bio-char
pyrolysis) and characterization of cocoa pod husks, an abundant agricultural biomass waste from Ghana, West
Africa, has been investigated and their potential as renewable feedstock for the production of high-value added
chemicals determined by analyzing chemical components of the derived bio-oil. GC–MS analysis of the bio-oil
indicated that major constituents were 9, 12-octadecadienoic acid and hexadecanoic acid”. Product distributions
revealed 58%wt. of bio-oil, 30%wt. of bio-char and 12%wt. of Non-condensable gas (obtained by difference).
Ultimate, proximate, structural composition, calorific value and thermogravimetry analyses were also performed
on the cocoa pod husks. Elemental analysis showed that the recovered milled cocoa pod husks contained about 7
elements potentially essential for plant growth.

1. Introduction
The rapid depletion of fossil fuel coupled with the quest to reduce
greenhouse gas emission has brought into focus the potential utilization
of renewable biomass as a sustainable energy feedstock, and for the
synthesis of “green” valuable platform chemicals (Amaniampong et al.,
2014, 2015; An et al., 2012). Biomass can be converted to bio-fuel and
bio-chemicals via different transformation routes, including physical,
biochemical and thermochemical transformation routes (Bridgwater
et al., 2002; McKendry, 2002; Tsai et al., 2017). Among these biomass
conversion processes, pyrolysis has attracted more interest particularly
to liquid fuel products due to its enormous advantages in transportation
and versatility in application such as turbines, boilers and combustion
engines, etc. (Bridgewater, 2004). The crude bio-oil can also be directly
used in boilers and turbines for heat and electricity generation and as
feedstock for the synthesis of platform chemicals (resins), fine chemi-
cals such as levoglucosan and fertilizers. Alternatively, they can be up-
graded either via chemical or physical means to more valuable
products. The production of biomass derived bio-oils and other pro-
ducts (char and gas) via pyrolysis of different biomass feedstock’s has
been extensively investigated, typically including woody biomass
(Demiral and Şensöz, 2008; Mohan et al., 2007), baggase (Asadullah
et al., 2007), beech wood (Demirbas, 2005), straws (Aho et al., 2008)
and municipal solid waste (MSW) (Asadullah et al., 2007; Jensen et al.,
2001; Pütün et al., 2006). Pyrolysis technology has the potential to
produce high value bio-oil capable of competing with and consequently
replacing non-renewable fossil fuels. The composition of the bio-oil
thereof produced, greatly depends on the conversion process utilized, as
well as the biomass source used. When pyrolysis bio-oils are the target
of production, the development of technologies based on fast pyrolysis
is sought in order to maximize the liquid fraction and to obtain bio-oils
of high quality. Fast pyrolysis technologies possess significant ad-
vantages over other biomass and waste processing technologies. Clas-
sical examples of the numerous advantages of fast pyrolysis are; easy
and cost-competitive storage and transportation of biomass and waste,
greater energy efficiency achieved in combustion processes, raw

⁎
Corresponding authors.
E-mail addresses: nasieduoe@yahoo.co.uk (N. Asiedu), prince.nana.amaniampong@univ-poitiers.fr (P.N. Amaniampong).

https://doi.org/10.1016/j.indcrop.2018.02.060
Received 28 October 2017; Received in revised form 12 February 2018; Accepted 16 February 2018
0926-6690/ © 2018 Published by Elsevier B.V.

Please cite this article as: Adjin-Tetteh, M., Industrial Crops & Products (2018), https://doi.org/10.1016/j.indcrop.2018.02.060
M. Adjin-Tetteh et al.
material processing can be decoupled from the final use of products and
facilitates the valorisation of delocalised biomass resources in small
scale autonomous installations, etc. (Bimbela et al., 2014). Reactor
types such as vacuum pyrolysis reactors, ablative pyrolysis reactors,
entrained flow reactors, fluidised bed, circulating bed and fixed bed
reactors, with varying configurations has also been reported for fast
pyrolysis technologies (Aho et al., 2008; Asadullah et al., 2007;
Bridgwater et al., 2002; Demirbas, 2005). Composition of the bio-oil
thereof produced, greatly depends on the conversion process utilized, as
well as the biomass source used.
In this study, we employed an abundant agricultural crop residue
generated from a cocoa plantation in Ghana as the sole biomass source
for fast pyrolysis upgrading. Cocoa makes a very important contribution
to the economy of Ghana with it, being the most important single ex-
port product in Ghana (Duku et al., 2011). The husk which is the main
residue generated during processing using the method of drying, when
compressed, can provide a source of alternative energy in the form of
bio-fuel. With an objective of reducing dependency on crude oil and
other related non-renewable energy sources, there have been a lot of
interests and investments in numerous renewable energy projects in
Ghana. Therefore, the onward transformation of cocoa pod husks, a
notable agricultural waste generated in huge amounts annually in
Ghana, into valuable chemicals and bio fuels, is particularly of enviable
interest. Cocoa pod husk, similar to other plant biomass, contains a
mixture of cellulose, hemicellulose, lignin, pectin and crude fibre, and
therefore serves as a potential source of biomass substrates for bio-
chemical production. The upgrading of cocoa pod husks to pyrolysis oil
is expected to contain several compounds such as ketones, carboxylic
acid, aldehydes, furans and phenols. Hence, the proper usage of the
husks could effectively provide economic advantages and decrease their
environmental impact. It is envisaged that, knowledge of the compo-
nents of the fast pyrolysis products from cocoa pod husk will serve as a
basis for the possible catalytic upgrading to produce other useful plat-
form chemicals in subsequent studies.
Fig. 1. (a) samples of cocoa pods, (b) dried cocoa pod husks, (c) milled cocoa pod husks.
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Industrial Crops & Products xxx (xxxx) xxx–xxx
2. Materials and methods
2.1. Biomass material
Cocoa pod husks were the main biomass agricultural wastes samples
investigated in this study. Samples (Fig. 1a) were obtained from an
agricultural farm at Effigyase, a town in the Ashanti Region of Ghana
and were sun-dried for approximately 1–2 weeks. The husks were then
reduced into smaller chips (Fig. 1b), ground with a mechanical grinder
and sieved to a fine size of less than 1 mm, precisely using a BS mesh
(Fig. 1c). The samples were then stored in sample bags and labelled
prior to further analysis.
2.2. Characterisation methods
2.2.1. Proximate analysis
In an effort to obtain information about the moisture, volatile, ash
and fixed carbon contents of the cocoa pod husks samples, proximate
analysis was performed following the British and European Standards
respectively. The fixed carbon contents were calculated by simple dif-
ference. The moisture content was determined as a constant weight loss
in a drying oven between 105 °C and 110 °C. Ash contents were also
determined as the residue after burning to constant weight at 600 °C
within 4 h, volatile contents were measured as weight loss after ex-
posing the sample to 900 °C within 10 min.
2.2.2. Ultimate analysis
Basic elemental compositions of the cocoa pod husks samples were
determined via an ultimate analysis. Typically, carbon, hydrogen, ni-
trogen and sulphur contents were determined by various analytical
methods and oxygen contents were obtained by difference.
2.3. Pyrolysis of cocoa pod husks
The pyrolysis experiments were carried out in a kiln reactor.
Scheme 1 explains that the system design for the pyrolysis of cocoa pod
husks in a kiln reactor. The feedstock was the same but the feed rate
was approximately 110 g/h. The temperature of the pyrolyzer was set
between 550 °C and 600 °C, with a heating rate of 400 °C/min and a
M. Adjin-Tetteh et al.
Scheme 1. Schematic representation of the kiln fast pyrolysis reactor set-up for the pyrolysis of cocoa pod husks.
vapour residence time of 2–4 min. The reactor length was 44.5 cm with
the inner diameter of 4.7 cm. For most of the experiments performed
the solid residence time was about 3.2 min. Pyrolysis reactions were
performed in triplicates.
2.4. Thermogravimetric analysis (TGA)-Differential thermal analysis
(DTA) of the raw cocoa pod husks
TA Instruments SDT Q600 apparatus equipped with TA Universal
Analysis software was used for DTA/TGA analysis of the raw cocoa pod
husks used in our pyrolysis investigations.
2.5. Bio-oil analysis
2.5.1. Gas chromatography–mass spectrometery analyses
Bio-oil and commercial products were analyzed on a Autosystem XL
– TurboMass (PerkinElmer). Before analysis, bio-oil was silylated.
Typically, a sample (0.1 g) was taken and diluted in 2 mL of a solution
of pyridine containing 1 mg/mL of sorbitol (internal standard). After
solubilization, 1.0 mL of Hexamethyldisilazane (HDMS, Sigma Aldrich,
reagent grade, ≥99%) and 1.0 mL of Trimethylchlorosilane (TMCS,
Sigma Aldrich, for GC derivatization, ≥99.0% (GC)) were successively
added. The solution was then centrifuged for 10 min and 0.1 μL of the
solution was injected, A HP5-MS column was used (L = 30 m,
Ø = 0.32 mm, e = 0.25 μm). The oven was heated from 80 °C to 220 °C
with a heating ramp of 10 °C/min, then to 320 °C with a heating ramp of
5 °C/min and hold for 10 min at 320 °C, carrier gas was helium (1 mL/
min). Injection was executed in splitless mode. Mass spectra detection
was undertaken with TurboMass (PerkinElmer). The ion source and
quadrupole analyser temperatures were maintained at 250° with a
solvent delay of 6 min was selected. Mass spectrometric ionization was
undertaken in electron ionization (EI) mode with an EI voltage of 70 eV.
Full scan monitoring was performed initially within the mass range of
50–600 amu. Data were collected and analyzed with the NIST library
software.
2.5.2. Bio-oil water content analysis
The water content of the bio-oils was determined by Karl Fisher
titration using ASTM D–1744. 5 mL of each bio-oil sample (triplicate
experimental crude products) was measured and titrated with a Karl
Fischer reagent. The end point of the solution was shown by an intense
colour change from yellow to brown. Information on the water content
can be useful in predicting the quality and performance characteristics
3
Industrial Crops & Products xxx (xxxx) xxx–xxx
of the bio-oils.
2.5.3. pH value, density and viscosity determination of bio-oil
A EUTECH Instruments 510 pH meter at room temperature was used
to determine the pH of the bio-oil. Prior to the measurement, the in-
strument was calibrated with liquid calibration standards of pH 4, 7 and
9. For the determination of the viscosity of the bio-oil, a Cannon-Fenske
up-flow viscometer was used. Typically, approximately 20 mL of the
bio-oil sample was placed in the viscometer and the flow was observed
at 22 °C. A density measurement was also performed in a 10 mL picn-
ometer following the ASTM D-369 standard. 10 mL of the bio-oil sample
was measured and weighed at 25 °C. The density was then calculated as
the weight of the bio-oil per unit volume. The procedure was performed
in triplicate to observe the consistency of the obtained results.
2.6. Fourier-transform infrared spectroscopy s (FT-IR) and X-ray
fluorescence (XRF) analysis
FT-IR analyses of milled cocoa pod husks, bio-oil and bio-char were
performed using PerkinElmer Spectrum One FT-IR spectrometer. X-ray
fluorescence (XRF) analysis was carried out on a Bruker AXS S4 ex-
plorer.
2.7. Heating value
The higher heating value (HHV) of bio-oil obtained was calculated
on a correlation developed by Channiwala and Parikh (2002) as shown
in Eq. (1):
HHVdry (MJ/
kg) = 0.3491C + 1.1738H + 0.1005S − 0.10340O − 0.151N −-
0.0211A (1)
The higher heating value on the as-produced (ap) bio-oil was esti-
mated using the Eq. (2) (Sheng and Azevedo, 2005) and taking into
account the water content of bio-oil (H2O, wt.%).
HHVap = HHVdry (1-H2O/100) (2)
3. Results and discussion
3.1. Characterisation of the cocoa pod husks
Moisture, ash, volatile and fixed carbon contents for the under-
M. Adjin-Tetteh et al. Industrial Crops & Products xxx (xxxx) xxx–xxx

Table 1 feedstock, the faster the ignition potential. However, the ash content
Proximate, Ultimate analysis (wt.%) and High Heating Value (HHV) (MJ/kg) of Cocoa measured in this study for cocoa pod husk was different from the lit-
pod husks investigated in comparison with literature reported data of Cocoa pod husks
erature reported values (Forero-Nuñez et al., 2015; Mansur et al., 2014;
around the world.
Ogunjobi and Lajide, 2015; Titiloye et al., 2013). Indeed, most reported
Proximate Analysis literature values reflects an ash contents of less than 10 wt.%, but in the
case of our analysis an ash content value of 16.24 wt.% was measured.
Moisture Volatile Ash Fixed Reference We attribute this difference in measured values of ash contents to the
matter carbona
difference in cultivation methods, environmental influences and greatly
Cocoa pod 11.07 61.73 16.24 10.96 This work due to difference in soil contaminations. Higher ash content has been
Cocoa podb 10.29 68.47 10.81 10.43 Titiloye et al. reported to be a result of higher level of inorganic compounds, which
(2013) can inherently act as catalytic effect on the global thermal conversion
Cocoa podc 11.53 58.46 13.21 16.8 Forero-Nuñez
technique. Conversely, high-ash content affects combustion character-
et al. (2015)
istics and reactor design, results in slagging, fouling and blocking pro-
blems in the reactor. Fixed carbon is undoubtedly the most valuable
Ultimate Analysis
parameter directly reflecting the energy potential of any biomass
C H S O N Cl HHV feedstock; therefore feedstocks with higher fixed carbon content possess
inherent higher heating values. The fixed carbon content observed for
Cocoa pod 48.70 0.75 0.97 48.39 1.19 n.d 12.48
our cocoa pod husk was 10.96 wt.%. The elemental compositions (wt.
Cocoa podb 43.87 5.82 0.57 47.28 2.23 0.23 17.08
Cocoa podc 43.87 5.84 0.17 37.20 0.17 n.d 18.10
%) of the cocoa pod husks used in our investigations are reported in
Table 1 (ultimate analysis), along with the heating value estimated
a
By difference. based on the results obtained via the elemental compositions and ex-
b
Samples obtained from Nigeria. perimentally (bomb calorimetry). Trace amounts of nitrogen (1.19 wt.
c
Samples obtained from Colombia.
%) and sulphur (0.97 wt.%) were observed in the sample. Conversely,
no trace amount of chlorine was found. Indeed, this is evident of the
investigated cocoa pod husks are shown in Table 1. Indeed, the fact that; cultivation, soil contamination and differences in crop loca-
moisture content of a potential fuel feedstock has been reported to be a tions vastly influence the elemental composition of the cocoa pod
crucial component, because it possesses a direct impact on the heating husks. Titiloye et al. (2013) reported a chlorine composition of 0.23 wt.
value (Bridgwater, 2012; Tsai et al., 2017). Thus, the lower the % in the cocoa pod husk samples obtained from Nigeria. Indeed, the
moisture content in the feedstock, the better it is for thermal conversion very low levels of sulphur and nitrogen observed in our cocoa pod husk
process. Also the higher the moisture content in the feedstock, the more feedstock is a major environmentally friendly indicator when com-
energy is wasted during thermochemical conversions of the raw ma- busted or during the utilization of its bio-derived products. As they can
terial. Nonetheless, moisture in the raw material can also act as both potential form environmental pollutants such as nitrous or sulphur
binding agents and lubricants, enhances gelatinization of starch and Oxides when present in the feedstock during combustion. More im-
facilitates the formation of van der Waals’ forces and possible diffusion portantly, the low levels of sulphur and nitrogen found in our samples
of water-soluble substances throughout the matrix of the raw material. are good indications that, the sample could be a potential source for the
Nevertheless, typically for thermochemical conversion processes, production of bio-oil for energy purposes. The higher heating value of
feedstock’s with lower moisture contents is often desired, whereas the cocoa pod husk investigated was 12.48 MJ/kg by calculations
higher moisture content is often preferred for biochemical conversion adopted from the formula by Channiwala and Parikh (2002), based on
processes. The results reported in Table 1 (proximate analysis) show the composition of main elements observed in the cocoa pod husks
that the moisture content obtained from the milled cocoa pod husk was during analysis. X-ray fluorescence spectroscopy (XRF) further revealed
approximately 11.07 wt.%. This was strikingly similar to that reported a cocktail of metal oxides present in our cocoa pod husks investigated.
for cocoa pod husks obtained from other parts of the world (Bridgwater, In brief, MnO (0.01 wt.%), Fe2O3 (0.01 wt.%), Na2O (0.26 wt.%), MgO
2015; Titiloye et al., 2013). Hence the feedstock under investigation (0.72 wt.%), Al2O3 (0.10 wt.%), SiO2 (0.29 wt.%), P2O5 (0.35 wt.%),
proves to be more suitable for thermal conversions technology, such as K2O (5.07 wt.%) and CaO (0.59 wt.%) were observed.
pyrolysis methods. It is worth stating that, climate and storage effects,
as well as difference in locations may accounts for the general trend and 3.3. Thermogravimetric analysis
slight differences in the moisture contents observed in our investiga-
tions as compared to those reported in literature. However, these results Thermogravimetric analysis (TGA) was utilized to obatain in-
are favourably comparable. formation on the thermal decomposition behaviour of the cocoa pod
husks. TGA pyrolysis (under argon) was set to operate from room
3.2. FT-IR analysis of the cocoa pod husks prior to pyrolysis temperature (20 °C) to 800 °C at low heating rate (10 °C/min). The
thermogravimetric (TG) and the derivative thermogravimetric (DTG)
Prior to pyrolysis of the cocoa pod husks, FT-IR analysis was per- plots of the cocoa pod husks are shown in Fig. 3(a) and (b) respectively.
formed on raw samples (Fig. 2). The peak observed around 3287 cm−1 Hemicellulose anc cellulose are the major composition of the volatile
depicts the OeH stretching vibration of hydroxyl functional groups matter, while lignin constitute the main composition for char formation
found in the cocoa pod husks. At around 2851–2919 cm−1, a CeH (Sanchez-Silva et al., 2012). These components have different on-set
stretching is also observed. The peak centered at 1615 cm−1 could be decomposition temperatures as a result of their composition and this
attributed to the C]O stretching of the samples and CeOeC stretching can be used to indicate the temperatures and regions of their elimina-
is also typical of the peak found at 1017 cm−1. tion from the sample under investigation. Stefani et al. (2005) reported
The volatile matter revealed a composition of 61.73% and was that, the sequence of degradation in lignocellulosic materials begins
measured on a dry basis. This was consistent with values reported in with the decomposition of hemicelluloses between the temperature
literature. Volatile matter composition has no remarkable effect on the ranges (150–350 °C). Followed by cellulosic material degradation in the
evolution of stronger bonds during densification or thermal conversions temperature range of 275–380 °C and lignin degrades between 300 and
of bio-derived substrates. However, it significantly affects the perfor- 500 °C. Oxidation of the fixed carbon also occurs from 500 to 600 °C
mance and physical stability of the solid bio-fuel during thermal con- with the resulting ash residue. This can be therefore be used to char-
version processes. Indeed, the higher the volatile matter in the acterize the degradation profile of the cocoa pod husks. Fig. 3(a) and

4
M. Adjin-Tetteh et al.
Fig. 2. FT-IR of raw cocoa pod husk.
Fig. 3. (a) TGA plot for cocoa pod husks (b) DTG plot for cocoa pod husks.
(b) reveal that there were 4 regions with differential quantities of
components eliminated by the thermal degradation process and these
can therefore be related to the different compositions of the cocoa pod
husks.
The weight loss in stage 1 (moisture evolution) was estimated as
12%. This was as a result of moisture elimination in the cocoa pod
husks during the initial degradation profile of the TGA analysis. Stage 2
of the weight loss regime (evolution of volatile component) was 48%,
5
Industrial Crops & Products xxx (xxxx) xxx–xxx
which can be attributed to the decomposition of hemicelluloses and
cellulose between 180 and 380 °C. Stage 3 is that of the oxidation of
fixed carbon on the cocoa pod husks (22%) and occurs between 400 and
600 °C, with the final stage (4) being the ash component as the final
residue which is composed of the inorganic elements (9%). The de-
gradation profile of the different compositions in the cocoa pod husks is
similar to profiles that have been reported in literature. Titiloye et al.
(2013) reported a similar thermal degradation profile in their work on
the thermochemical characteristic of some agricultural waste from West
Africa. Comparing the results in their investigations with that obtained
in our present study, it is observed that the percentage moisture content
of the cocoa pod husks (12%) was marginally higher than that reported
for the various agricultural wastes such as corn cob (8.72%), rice straw
(7.23%), corn straw (9.15%), moringa (10.38%) and sugar cane bag-
gase (8.52%). The percentage volatile matter component of the cocoa
pod husks was also lower than those of moringa cakes (75.08%), Par-
inari fruit shell (78.17%), corn straw (75.02%), corn cob (80.72%),
Jatropha cakes (72.53%) and rice husk (58.22%). However, the volatile
content of the cocoa pod husks was similar to that of rice straw
(45.68%) (Titiloye et al., 2013). The percentage fixed carbon of the
cocoa pod husks (22%) was higher than thos of all the agricultural
wastes; corn straw (9.70%), corn cob (7.60%), rice straw (1.33%), rice
husk (8.48%), moringa cakes (8.26%), Parinari fruit shell (14.51%)
reported by Titiloye et al. (2013). However, the fixed carbon of the
cocoa pod husks was similar to that obtained for sweet potato peel
residue (20.5%) (Asuquo and Martin, 2016). Finally, it was found that,
the percentage ash content of the cocoa pod husks (9%) was higher than
those of corn straw (6.13%), corn cob (2.93%) and jatropha cakes
(6.47%). But significantly lower than those of rice straw (45.76%), rice
husk (24.71%), sweet potato peels (11.2%) and cocoa pod husks
(10.81%) reported by Titiloye et al. (2013), and Asuquo and Martin
(2016).
3.4. Pyrolysis of cocoa pod husks and analysis of pyrolysis products
The cocoa pod husks were pyrolysed in a kiln reactor at a tem-
perature range of 550–600 °C. The pyrolysis products (bio char and bio-
oil) (Fig. 4i and ii) were recovered and thoroughly analyzed by GC–MS
and FT-IR. Analysis of the pyrolysis products showed 58 wt.% bio-oil,
30 wt.% bio-char and 12 wt.% Non-condensable gases (NCG obtained b
difference). Furthermore, the bio-char was explored as possible poten-
tial catalyst support for the onward catalytic conversion of the obtained
bio-oil into other valuable chemical (although this was out of the scope
of this current investigation).
The FT-IR analysis of the bio-oil (Fig. 5a) shows a characteristic and
conspicuous peak at about 3350 cm−1. This is could be ascribed to the
presence of eOH band stretching. The peak centered at 2110 cm−1 is
typical of sp C^C stretching. The band appearing at 1634 cm−1 is
M. Adjin-Tetteh et al. Industrial Crops & Products xxx (xxxx) xxx–xxx

Fig. 4. (i) Bio-Oil, (ii) Bio-char.

Fig. 5. (a) FT-IR Spectra of the bio-oil from dried cocoa milled husk. (b) FT-IR Spectra of the bio char from dried cocoa milled husk.

Table 2 FT-IR analysis of the bio-char (Fig. 5b) revealed a pronounced peak
Characteristics of bio-oil obtained from fast pyrolysis of cocoa pod husks. around 3339 cm−1. This show the existence of hydroxyl groups on the
bio-char. The peak at 1628 cm−1 could be ascribed to the C]C
Bio-oil Calorific Calorific Water Density Viscosity pH
yield value, value, content (kg m−3) (mm2 s−1) stretching of the aromatics, whereas the peak around 1370 cm−1 could
(wt.%) HHVdry HHVar (MJ/ (wt.%) correspond to the CH3 deformation of the bio-char sample. The CeOeC
(MJ/kg) kg) stretching band is typical of the peak observed at 1004 cm−1 and the
peak at 871 cm−1 could also be attributed to the CeH out-of-plane
58 12.48 8.64 30.8 1150 140 2.8
bending.
In the investigations of these spectra regions of the raw cocoa pod
indicative of a carbonyl group. The band stretching appearing around husks, bio-oil and bio-char described above, FT-IR analysis might serve
1413 cm−1 could also suggest the presence of a carboxylate. The bands as a potential fast screening technique to identify the extent of carbonyl
appearing between 1052 and 1276 cm−1 is an indicative of a typical group or oxygen content in the samples.
CeO stretch such as a glycosidic bond linkage. In fast pyrolysis of bio-derived feedstock, liquid bio-oil is generally

6
M. Adjin-Tetteh et al. Industrial Crops & Products xxx (xxxx) xxx–xxx

Fig. 6. GC–MS analysis of (a) bio-oil sample and (b) authentic 9, 12-octadecadienoic acid.

obtained as the main reaction product, while solid char and volatile from the pyrolysis reaction, called “reaction water” and the higher the
gases are valuable by-products. However, the bio-oil obtained via fast reaction water yields, the higher the water content in the bio-oil. The
pyrolysis often contains significant amount of water as a result of the quality and use of bio-oil is dependent on its water content, which can
moisture content in the biomass feedstock and also the water produced be either advantageous or disadvantageous. Higher bio-oil water

7
M. Adjin-Tetteh et al.
Table 3
Tentative compounds in Cocoa Pod Husks bio-oil using GC–MS.
tR (min) Tentative compound assignment Peak area (%)
6.24 2-oxo-propanoic acid 3.28
9.04 4-hydroxy-3-penten-2-one 2.48
11.01 Octanoic acid 1.96
13.25 2-butenedioic acid 5.63
15.99 Azelaic acid 2.17
17.84 Sorbitol (Internal Standard) 8.98
18.61 Hexadecanoic acid 13.15
20.39 9,12-octadecadienoic acid 53.27
20.52 Linolenic acid 5.25
21.89 Hexanoic acid 3.82
tR = Retention time, sorbitol was used an internal standard.
content improves bio-oil flow characteristics by reducing viscosity.
Water also leads to a more uniform temperature profile in the cylinder
of a diesel engine as well leads in reductions in NOx emissions (Czernik
and Bridgwater, 2004). On the other hand, the presence of water in bio-
oil reduces the heating value, especially the LHV and flame temperature
of bio-oils (Czernik and Bridgwater, 2004). The water content of bio-oil
produced from the cocoa pod husks used in this investigation estimated
via the Karl Fischer titration method was 30.8 wt.%. The water content
of bio-oil obtained in our investigation is marginally higher than those
obtained from the pyrolysis of woody biomass, which were found to be
in the range of 15–30 wt.% (Czernik and Bridgwater, 2004). Water
contents in the range of 25–45 wt.% has also been reported for rice
straw derived bio-oils at fast pyrolysis temperatures of in the range of
412–598 °C (Lee et al., 2005). The water content of the cocoa pod husk
bio-oil appeared to be in the middle range of those obtained by Lee
et al. (2005) and also in perfect agreement with the water content
obtained from cassava stalk (30.87 wt.%) and cassava rhizome
(31.33 wt.%) at a pyrolysis temperature of 502 and 510 °C, respectively.
Nonetheless, the water content obtained in our investigation (30.8 wt.
%) can be regarded as high and may need to be significantly reduced
prior to use.
The bio-oil obtained from the fast pyrolysis of cocoa pod husks was
acidic in nature with a pH of 2.8. This pH value is similar to the pH
values obtained for wood-derived bio-oil (pH = 2.5) via fast pyrolysis
(Czernik and Bridgwater, 2004) but lower than that obtained for rice
straw-derived bio-oil (pH = 4.2) (Pütün et al., 2004). The low pH value
of the cocoa pod husk-derived bio-oil suggest the presence of carboxylic
acid compounds, which was further confirmed by GC–MS analysis
(discussed later in the manuscript). pH value is one of the crucial bio-
oils properties, because it is an intrinsic indicator of their corrosiveness.
Severe corrosion of vessels can occur as a result of the acidic properties
of bio-oils. The determination of pH value bio-oils gives a good in-
dication of the choice of equipment materials, such as stainless steel
and olefin polymers to handle bio-oils with low pH values (Bridgwater
et al., 1999). Noteworthy, the density and viscosity values of the bio-oil
was measured as 1150 kgm−3 and 140 mm2 s−1, respectively.
The higher heating value of the as-produced (HHVap) bio-oil was
calculated taking into account the water content of the bio-oil (H2O, wt.
%). The HHVar was calculated to be 8.64 MJ/kg. A summary of the bio-
oil analysis data is shown in Table 2.
GC–MS analysis (Fig. 6), was carried out in order to get an idea of
the nature and type of organic compounds in the pyrolysis liquid pro-
duct. The analysis revealed a total of 10 tentative compounds of the
pyrolysis bio-oil, which are the most probable compounds identified by
the MS search file (HP MS ChemStation), among which is 9, 12-octa-
decadienoic acid having about 53.3% relative content (peak area per-
cent) (Table 3). The presence of 9, 12-octadecadienoic acid was further
confirmed by running GC–MS analysis on 9, 12-octadecadienoic acid
reagent grade (Sigma Aldrich, ≥99.0%) which appeared to have a si-
milar retention time (tR) as that obtained for the bio-oil analysis.
8
Industrial Crops & Products xxx (xxxx) xxx–xxx
Noteworthy, two isomers of 9, 12-octadecadienoic acid was observed
for the GC–MS analysis of the Sigma Aldrich reagent grade sample.
4. Conclusions
Thermal conversion of locally generated cocoa pod husks from
Effigyase, a farming district, in the Ashanti region of Ghana has been
attempted as a potential agricultural waste source for bio-oil production
via fast pyrolysis process. The cocoa pod husk was prior to pyrolysis
thoroughly characterized by proximate, ultimate, heating value, ther-
mogravimetry and FT-IR analysis. Pyrolysis products (bio-oil and bio-
char) were also hitherto characterized. Proximate analysis yielded re-
sults comparable to similar agricultural waste from other regional parts
of the world. The unusual high ash content (16.24 wt.%) obtained in
our cocoa pod husk could fairly explain the comparably low value
observed for the high heating value (12.48 MJ/kg) estimated in our
investigation. The high water content of the bio-oil (30.8 wt.%) resulted
in a low value observed for the high heating value of the as-produced
bio-oil (HHVap, 8.64 MJ/kg). The high amount of volatile matter ob-
served is good indication of better combustibility, gasification and
pyrolysis, when the sample is used as potential bio-energy feedstock.
The basic elemental analysis revealed that the sample investigated
possessed a comparably lower amount of hydrogen and rather high
amount of oxygen and carbon. The levels of nitrogen and sulphur
contents in the samples were however found to be very low, with no
trace amount of chlorine. This is a good indication of an en-
vironmentally friendly energy feedstock during combustion of the raw
material or its biomass derived products. The thermogravimetric ana-
lysis further indicated that the cocoa pod husk is indeed an excellent
feedstock for pyrolysis reactions. The obtained bio-oil was acidic with a
pH of 2.8, density of 1150 kg m−3 and viscosity of 140 mm2 s−1, was
observed to be rich in 9,12-octadecadienoic acid, a valuable carboxylic
acid was observed to be a major composition of the as-produced bio-oil
from the cocoa pod husks. Future experiments will be focused on the
potential use of the obtained bio-char as catalytic support material for
the direct conversion of the bio-oil into more valuable chemicals.
Conflict of interest
Authors also declare no conflict of interest.
Acknowledgements
The authors express profound appreciation to the local farmers of
the Effiduase community, Kumasi-Ghana, for providing the raw cocoa
pod husks needed for this investigations. The authors also would like to
indicate that, this work was not funded by any funding agency.
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