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Coconut shell bio-oil distillation: Its characteristic and product distribution

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Apip Amrullah at Lambung Mangkurat University
Apip Amrullah
Eko Teguh
Eko Teguh
Eko Teguh
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Abstract

The properties of bio-oil distillation and product distribution are critical for parameter optimization and reaction conditions. In this work, low-reaction temperature of 96, 97, 98, 99, and 100 °C was conducted. The slow pyrolysis process at 500 °C with a 1 hour holding period yielded the coconut shell bio-oil employed in this research. The characteristic components of bio-oil were thoroughly evaluated using gas chromatography-mass spectrometry (GC-MS). The research founded that during the distillation reaction process, a similar critical point was thoroughly established, which might be attributed to the steady system created by the hydroxyl group. As a result, bio-oil distillation might be divided into 3 stages: steady, explosive, and heating. The content of acetic acid, 2-Furancarboxaldehyde, and phenol are dominated. Acetic acid yield showed an increase, followed by the distillation reaction temperature. Phenol yield was also observed as a dominant product in the bio-oil. The higher phenol yield was observed at a temperature of 98 o C is 38 %. The observed phenomena could be related to the oxidation of hemicellulose, cellulose, and lignin to form phenol, the bio-major oil component. The specific distillation properties and product distribution provide a great look at the reaction process and component enrichment patterns, which can aid formulation and parameter adjustment.
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IOP Conference Series: Earth and Environmental Science
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Coconut shell bio-oil distillation: Its characteristic
and product distribution
To cite this article: Apip Amrullah and S. Eko Teguh 2022 IOP Conf. Ser.: Earth Environ. Sci. 1038
012018
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AESAP-2021
IOP Conf. Series: Earth and Environmental Science 1038 (2022) 012018
IOP Publishing
doi:10.1088/1755-1315/1038/1/012018
1
Coconut shell bio-oil distillation: Its characteristic and product
distribution
Apip Amrullah, Eko Teguh S.
Department of Mechanical Engineering, Lambung Mangkurat University,
Jl. Brigjen H. Hasan Basri, Kayu Tangi, Banjarmasin, Indonesia
Email: apip.amrullah@ulm.ac.id
Abstract. The properties of bio-oil distillation and product distribution are critical for parameter
optimization and reaction conditions. In this work, low-reaction temperature of 96, 97, 98, 99,
and 100 °C was conducted. The slow pyrolysis process at 500 °C with a 1 hour holding period
yielded the coconut shell bio-oil employed in this research. The characteristic components of
bio-oil were thoroughly evaluated using gas chromatography-mass spectrometry (GC-MS). The
research founded that during the distillation reaction process, a similar critical point was
thoroughly established, which might be attributed to the steady system created by the hydroxyl
group. As a result, bio-oil distillation might be divided into 3 stages: steady, explosive, and
heating. The content of acetic acid, 2-Furancarboxaldehyde, and phenol are dominated. Acetic
acid yield showed an increase, followed by the distillation reaction temperature. Phenol yield
was also observed as a dominant product in the bio-oil. The higher phenol yield was observed at
a temperature of 98 oC is 38 %. The observed phenomena could be related to the oxidation of
hemicellulose, cellulose, and lignin to form phenol, the bio-major oil component. The specific
distillation properties and product distribution provide a great look at the reaction process and
component enrichment patterns, which can aid formulation and parameter adjustment.
1. Introduction
Renewable energy production is gaining popularity as a technique of decreasing pollution and attaining
a long-term aim. Biomass can be utilized to generate energy and chemicals using pyrolysis technology,
which is a valuable renewable resource (bio-oil, charcoal, and syngas) [1–4]. However, crudes bio-oil,
a low-quality by-product of thermal decomposition, cannot be used in engines. [5–7]. As a result, along
with its low price and availability of use, bio-oil distillation process is one of the technologies for
enhancing bio-oil quality, is commonly utilized to upgrade bio-oil [8,9]. Bio-oil was originally
supposed to be a substitute for petroleum fuels due to its similar appearance and properties. Bio-oil
needed to be refined before it could be used as a drop-in fuel because of its fluidity, calorific value,
and corrosiveness [10]. Researchers have developed a number of upgrading processes, including
catalytic cracking, catalytic pyrolysis, hydrodeoxygenation, supercritical fluids, and esterification
[11,12]. Nevertheless, harsh circumstances, difficulties in controlling, expensive equipment costs, and
low conversion rates hampered bio-oil commercialization. Furthermore, the commercial prospects for
bio-oil as a fuel were clouded by the continued low worldwide crude prices. As a consequence, the
chemical feedstock might be used to make commercial bio-oil.
Phenol, acetic acid, eugenol, guaiacol, and levoglucosan are among the high-value-added
compounds present in bio-oil [13]. As a result, it's presently one of the much potential low-cost fine
chemical raw materials available. Condensation, centrifugation, extraction, and distillation are some
of the extraction and filtration process that have been used on bio-oils in previous work [13–16].
However, distillation appears to be one of the most promising technologies among the many available,
given its low price and potential for large-scale application. Distillation could evaporate low-boiling
AESAP-2021
IOP Conf. Series: Earth and Environmental Science 1038 (2022) 012018
IOP Publishing
doi:10.1088/1755-1315/1038/1/012018
2
elements to produce component distinction and purifying depending on difference in boiling points of
various substances [17]. Distillation was extensively used in the oil refining and fine chemical plants
since it did not involve any extra solvents and prevented the introduction of new contaminants.
Consequently, with a well-established separation process, distillation can separate and purify bio-
oil, and several researchers have attempted to upgrade bio-oil using distillation. Choi et al. [18] used
suction simple distillation to evaluated the composition and properties of crude bio-oil from brown
algae. Tao et al. [19] thought that a multi-step distillation separation could help solve the bio-oil
heterogeneity problem. Huang et al. [20] used a fluidized bed reactor to perform hydrothermal process
and liquid - liquid extraction of rice husks, and they examined at the effects of the different parameters
on product distributions. Nonetheless, to the best of authors knowledge, most research focus on
percentage and product quality in relative temperature ranges, with just a few complete investigations
on bio-oil distillation products and characteristic outside a range of temperatures. To the best of the
authors’ knowledge, such a upgrading process is still unexplored in the available literature. Therefore,
the aim of this to evaluated the effect of distillation temperature (96, 97, 98, 99, and 100 °C) on the
products distribution and bio-oil characteristic produced from coconut shell. Hence, the thorough
investigation of coconut shell bio-oil distillation would be beneficial not only for environmental
mitigation but also for producing bioenergy and value-added chemicals and providing a more profound
understanding for future research and implementation.
2. Materials and Methods
2.1. Feedstock
The bio-oil feedstock used in this research was produced from slow pyrolysis of coconut shell using
the reactor with 2 kg/h production capacity with the temperature reaction of 500 oC. To avoid unwanted
degradation, the feedstock was stored at 10 °C after filtration. The ultimate analysis of coconut bio-oil
was conducted previously by Thamizhvel et al. [21]. The C contained was 64 %, H (5.1 %), N (2.4
%), O (29 %), and S (0.03 %), respectively. The volatile matter and fixed carbons were 52 wt% and
46 wt%, respectively.
2.2. Distillation process
A lab-scale distillation device was installed (Fig.1).
Fig.1. Photo of distillation equipment
To optimize for the temperature and minimize steam condensation on the inner pipe, a silicone heating
connection was wrapped around the distillation head. Throughout the heating phase, the silicone
heating connection was kept at a constant temperature of 100 °C. In this work, 100 g bio-oil feedstock
was placed in a flask, and the reaction temperature was adjusted at 96, 97, 98, 99, and 100 °C,
respectively. To achieve thorough distillation, the reaction period was set to 2 hours. After collecting
the components and separating them into oil and aqueous phases, these were preserved. Experiments
were carried out twice in order to minimise the errors.
AESAP-2021
IOP Conf. Series: Earth and Environmental Science 1038 (2022) 012018
IOP Publishing
doi:10.1088/1755-1315/1038/1/012018
3
2.3. Analytical method
The GC-MS analyzer used in this study was pointed out by Amrullah et. al. [22]. The furnace box's
heating technique was to keep it at 40°C for 2 minutes, then raise it to 180 °C at 3 °C/min for 2 minutes,
then to 280 °C for 3 minutes at 10 °C/min. The target compounds were identified and quantified using
standard chemicals and/or the NIST mass spectral library.
3. Results and Discussion
3.1. Effect of distillation temperature on product distribution
Fig. 2 showed the effect of distillation temperature (96, 97, 98, 99, and 100 oC) on the product
distribution of bio-oil (bio-oil, solid, and gaseous). The temperature is important in supplying the heat
required for biomass decomposition. Temperature changes enhance bio-oil and gaseous yield.
Fig. 2. Effect of temperature on product distributions
Bio-oil increased from 37-50 % by increasing temperature from 96-100 oC. Meanwhile,
increasing the temperature from 96 to 100 oC reduced solid yield from 3 to 1.5 %. These findings
followed with prior research that found that the degradation of volatiles, which thermally decompose
into low molecular weight liquids and gas components as lignocellulosic biomass decomposes, is
connected to a reduction in char yield as temperature rises [23,24].
3.2. GC-MS analysis of distilled bio-oil
This research examined through into effect of temperature distillation on bio-oil characteristics. Table
1 shows the general chemicals identified by GC-MS.
AESAP-2021
IOP Conf. Series: Earth and Environmental Science 1038 (2022) 012018
IOP Publishing
doi:10.1088/1755-1315/1038/1/012018
4
Table 1. Compound identified in coconut shell bio-oil by GC-MS
No
Compounds name
Formula
Percentage under different distillation
temperature
96 oC
97 oC
98 oC
99 oC
100 oC
1
Acetaldehyde
C₂H₄O
1.66
0.21
n/a
n/a
n/a
2
Pentalenone
C8H6O
10.95
n/a
n/a
n/a
n/a
3
N-ethyl-N-nitroso-
C3H7N3O2
10.75
n/a
n/a
n/a
n/a
4
2-Butanone
C4H8O
22.19
n/a
0.34
0.38
n/a
5
Acetic acid
CH₃COOH
14.06
n/a
46.36
51.8
65.45
6
Propanoic acid
C₃H₆O₂
4.26
3.21
2.94
3.21
3.01
7
2-Butenal
C4H6O
0.49
n/a
n/a
n/a
n/a
8
Ethanol
C2H5OH
1.89
n/a
n/a
n/a
n/a
9
Butanoic acid
C4H8O2
0.95
n/a
1.12
1.06
n/a
10
3-Penten-2-one
C5H8O
0.44
n/a
2.19
2.32
n/a
11
FURAN
C4H4O
0.53
n/a
n/a
n/a
n/a
12
1,3-Dioxolan-2-one
C3H4O3
0.74
n/a
n/a
n/a
n/a
13
Cyclopentanone
C5H8O
2.93
n/a
n/a
n/a
n/a
14
2-Furancarboxaldehyde
C10H8N2O2
10.88
10.43
0.33
n/a
n/a
15
2-Pentanone
C5H10O
0.26
2.29
2.94
3.59
n/a
16
2-Cyclopenten-1-one
C5H6O
1.27
1.18
0.43
1.81
0.95
17
Ethanone
C5H8O
1.26
1.47
0.72
0.28
n/a
18
Phenol
C6H6O
13.85
36.27
38.34
34.74
27.82
19
2,3-Dimethyl-2-cyclopenten-
C7H10O
0.24
0.36
0.36
0.28
n/a
20
2-Methoxy-4-methylphenol
C8H10O2
0.41
0.85
0.85
0.51
n/a
From table above showed that the main compounds were acetic acid, propanoic acid, 2-
Cyclopenten and phenol. Meanwhile, butanoic acid, 3-penten-2-one, 2-Furancarboxaldehyde, 2-
Pentanone, 2,3-Dimethyl-2-cyclopenten, and 2-Methoxy-4-methylphenol were obtained as a side-
products of ketone and phenolic compounds. In this study, acetic acid was the most prevalent
component in the bio-oil product. When the temperature was elevated, the output of acetic acid
increased from 14 to 65 (wt%), showing that lignin and hemicelluloses were degraded to create acetic
acid [25,26]. The decomposition of lignin can generate not even just acid but also phenol. According
to Zhang et al. (2012), thermal decomposition of lignin generates phenol in two steps: firstly, lignin
decomposes into different phenolics; secondly, phenol compounds undergo decarboxylation,
demethylation, and other phenol reactions to produced phenol [27].
4. Conclusion
The characteristics and distribution of compounds during the distillation process of bio-oil are
examined in this study. Based on functional groups, the compounds in the fraction were divided into
7 chemical groups: aldehyde, ketone, acid, butanol, ethanol, furan, and phenol. The maximum bio-oil
yield of 50% was obtained at 100 ° C. The bio-oil phase has a phenol content of up to 38 %. The
oxidation of cellulose, hemicellulose, and lignin to produce phenol, which is the major component of
bio-oil, could explain the observed behaviors.
AESAP-2021
IOP Conf. Series: Earth and Environmental Science 1038 (2022) 012018
IOP Publishing
doi:10.1088/1755-1315/1038/1/012018
5
5. Acknowledgement
The present study was supported by Mechanical Engineering Department, Lambung Mangkurat
University, Banjarmasin, Indonesia.
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... Furthermore, research has demonstrated that bio-oil can be blended with glycerol and methanol within specific ratios to create homogeneous fuel mixtures, underscoring the intricate balance required for optimal performance [7]. Studies have also explored the fate of bio-carbon in co-processing products, shedding light on the distribution of biocarbon in different fractions of the final products [11][12][13]. Moreover, investigations into the utilization of bio-additives in gasoline engines have shown promising results in terms of improving engine torque, efficiency, and combustion characteristics [14]. ...
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  • Apr 2020
  • ENERGY
A two-stage pyrolysis of wood was conducted to produce a phenol-rich bio-oil. The two-stage pyrolysis process included auger and fluidized bed reactors connected in series. In this study, the effects of temperatures of the auger and fluidized bed reactors and the type of fluidizing medium were mainly investigated. The auger reactor temperature was varied from room temperature to about 290 °C, whereas the fluidized bed reactor temperature ranged from about 500 to 700 °C. As the auger reactor temperature rose from about 20 to 290 °C, the gas yield increased from 27 to 31 wt%. At about 290 °C, the production of phenol was greatly enhanced. A high fluidized bed reactor temperature favored the formation of phenol, efficiently exploiting the weakened bond strength between C (benzene) and methoxy group of lignin molecules caused by heat treatment in the auger reactor. The use of nitrogen as the fluidizing medium drastically increased phenol production, which was achieved by reducing reactions of phenol produced inside the fluidized bed reactor with other components. In the current study, the maximum phenol content in bio-oil reached about 16 wt%. Bio-oil with a high phenol content has good potential as a reactant in the phenol resin synthesis.
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A centrifugation-first approach for recovering high-yield bio-oil with high calorific values in biomass liquefaction: A case study of sewage sludge
Article
  • Nov 2019
  • FUEL
A new “centrifuge-first” approach was developed to recover a large amount of bio-oil produced during hydrothermal liquefaction (HTL) of dewatered sewage sludge (DWSS). The entire mixture produced from HTL was first centrifuged to separate the water + water-soluble organics (WSOs) phase from the bio-oil (BO) + solid residue phase, and subsequently, bio-oil was separated from solid residue by simple filtering. The HTL of DWSS at an optimum condition of 325 °C and 12–14 MPa for 30 min resulted in a DWSS conversion of 88%. Under this optimum condition, using the centrifuge-first approach, the yield of bio-oil recovered was 64 wt%, a value that was much higher than that of LLE with dichloromethane (47 wt%) or ethyl acetate (41 wt%). The centrifuge-first approach can be applied to recover bio-oil produced at a variety of HTL parameters, including temperature (300–400 °C), time (30–120 min), and pressure (25–36 MPa). The O/C ratios, calorific values of the bio-oils, and average molecular weights were in the range of 0.03–0.05, 33–36 MJ kg⁻¹, and 130–190 g mol⁻¹, respectively, demonstrating that they were not very sensitive to the process parameters. In addition to the high energy content, the low water content (<1 wt%), low inorganic content (<1 wt%), and low acidity (total acid number <26 mg KOH per g oil) in the bio-oil recovered from the centrifuge-first approach make its use in combustion fuel applications suitable. The major composition of the bio-oils was aromatics, N-cyclic species, and long-chain hydrocarbons.
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Kinetics, thermodynamics, and physical characterization of corn stover (Zea mays) for solar biomass pyrolysis potential analysis
Article
  • Mar 2019
  • BIORESOURCE TECHNOL
Solar pyrolysis of agricultural waste has huge potential for sustainable production of fuel and chemical feedstock. In this paper, the kinetics, thermodynamics, and physical characterization of corn stover (CS) collected from Wyoming, USA was conducted with respect to solar pyrolysis. The kinetics and thermodynamics of the CS pyrolysis was analyzed in detail using the methods described by KAS (Kissinger-Akahira-Sunose) and FWO (Flynn-Wall-Ozawa), from which the activation energy, Gibbs energy, Arrhenius pre-exponential factor, enthalpy, and entropy were derived.14 other kinetics models based on reaction order, diffusion, nucleation, geometric contraction, power models were also examined, and models based on diffusion was found to be best suited. The CS was used for solar pyrolysis of biomass and the products were analyzed by mass spectroscopy, ICP-MS, GPC, micro-GC, and Elemental analyzer. The results show that CS is suitable for solar pyrolysis to produce chemicals and other fuels.
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Influence of temperature and duration of Pyrolysis on the property heterogeneity of rice straw biochar and optimization of pyrolysis conditions for its application in soils
Article
  • Jan 2019
  • J CLEAN PROD
This study investigated the effects of temperature and heating duration of the pyrolysis on the yield and properties of the biochar. Also, this study uniquely investigated the growth of mung beans germinated at five different pH conditions (4, 6, 7, 8, and 10) using extracts of biochar produced at four different pyrolysis temperatures (400°C, 500°C, 600°C, and 700°C) for three different heating durations (60, 90, and 120 minutes). Biochar solvent extraction was done by mixing a predetermined doze of biochar to solutions initially maintained at five different pH conditions. The biochar extracts were also characterized for its pH, EC and nutrient values and correlated with the germinated seed lengths. Further, this study based on the results of seed germination optimized the biochar production conditions with such properties to promote maximum seedling growth. Results showed that the yield of biochar decreased from 45.04 % to 33.45 % as temperature raised from 400°C to 700°C. The properties of biochar are primarily affected by the temperature as compared to the heating duration of the pyrolysis. The crystallinity index in the biochar decreased by 15.25 % with the increase in the temperature from 400 ˚C to 700˚C. Correlation test among seed lengths and biochar extracts properties showed that the seed growth was directly correlated with the increase in the nutrient values at all pH conditions. Based on the germination test, the optimized conditions for the maximum seedling growth observed as pH range (8 – 9), high nutrient, CEC, and ash content, and low VM content and their respective temperature and heating duration range modelled as 450°C - 550°C and 100 – 110 minutes respectively.
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