Waste to green fuels: Kinetic study of low lipid waste algae for energy development

Article Detail:
Authors - C.N. Kowthaman , V. Arul Mozhi Selvan
Name of Journal- Bioresource Technology Report,
Volume - 11 (2014),
Period of Publication –December 2020,
Pages- 174–180
Web Link: https://doi.org/10.1016/j.biortech.2014.02.023

Suvranil Banerjee
ROLL NO: 002230601001
Academic Session : 2022-2023
Semester :1st
Master of Technology – Energy Science and Technology
School of Energy Studies
Jadavpur University
26th December 2022
Introduction
• The everlasting climatic change and the high dependency of fossil fuel led the researchers to find the
potential alternative sources of cleaner energy productions (Chowdhury et al., 2019). As a renewable
resource, biomass is becoming a valuable candidate for a fuel source, and it is also attracted as a sub-
stitute for conventional petro-diesel fuel (Maurya et al., 2016).
• Generally, biomass consist of three different groups, such as first-generation, second-generation, and
third-generation feedstock's (Kowthaman and Varadappan, 2018; Yew et al., 2019).
• The first-generation feedstocks are derived from edible sources such as corn, wheat, potato, palm oil,
soybean, and sugarcane, etc. which are cultivated in the arable land, and has the disadvantages on
food security, soil erosion, deforestation, and poor energy balance. This leads to an accumulation of
harmful contaminations such as ammonia and nitrous oxide in both water, and land (Kowthaman and
Varadappan, 2019; Digambar et al., 2020).
• The second-generation feedstock's originated from non-edible sources, animal wastes, and lignocellu-
lose materials such as municipal solid waste, Pongamia pinnata, Jatropha Curcus, grasses, and sewage
solid waste, etc. which produce higher biofuels in less arable land but they encounter economically un-
viable due to pretreatment, transportation, and difficult in the collection (Kowthaman and Varadappan,
2018; Digambar et al., 2020).
Micro-alage as 3rd Generation Feedstock

• In recent years. Microalgae are considered as a third-generation feedstock due to its promis-
ing sustainable source for biofuel production that produces 23 times higher yield than palm
oil. Microalgae has a heating value, and oil yield of 24 MJ/kg, and 136,900 L/ha respectively
which is higher than the other biomass such as castor oil with 1413 L/ ha, coconut with oil
yield of 2689 L/ha, Jatropha yields 2420–2970 L/ ha, Karanja with 5500 L/ha, sunflower pro-
duces 952 L/ha, safflower yields 779 L/ha. The major compositions of microalgae are Lipids 7–
23 wt%, carbohydrates 5–23 wt%, and protein is 6–52 wt% (Ismail and Al-Zuhair, 2020; Chisti
(2007); Sanchez-Silva et al., 2013).
• In addition to that, microalgae have a lot of advantages such as higher growth rate, high effi-
ciency in photosynthesis, CO2 fixation, and carbon sequestration. Besides integrated cultiva-
tion of algae using coal-based power plants, not only reduced the green-house gases but
also used for carbon sequestration, and utilization. Recently, chimney gases added with 3–
6%v/v of carbon-di-oxide cultivation systems reported that increased in biomass yield (Zhao
et al., 2019).
• Microalgae biomass can be potentially converted into solid, liquid, and gaseous form of
bioenergy through biochemical and thermochemical conversion techniques (Demibras (2000);
Zhao et al., 2019). Kumar et al. (2017) reported thermochemical methods such as combustion,
pyrolysis, hydrothermal liquefaction, direct liquefaction, and gasification has been intensively
Micro-alage as 3rd Generation Feedstock
• Among these, gasification includes partial oxidation at elevated temperatures from 800 to 900 °C to convert
biomass into synthetic gas. Whereas, combustion converts the biomass into useful energy at high temperature
(> 1000 °C) under excess oxygen (Agarwal and Chakraborty, 2013). However, the biochemical conversion of
biomass into value-added products has not been commercially feasible due to the inherent potential of the bio-
logical reaction during fermentation, and anaerobic digestion process (Robert et al., 2017).
• Pyrolysis process is divided into fast and slow pyrolysis; when microalgae are treated with slow pyrolysis, an oil
yield of 43, and 31.1% were reported for fresh and oil extracted biomass. During pyrolysis, biochar, a solid
product was found that contains minerals and trace metals, which are two major ingredients for the building
blocks structure and chemical composition (Hong et al., 2020; Radhakumari, 2015).
• However, it is difficult to study the kinetics of pyrolysis because of the simultaneous change in the physical and
chemical properties of microalgae. But by optimizing the heating rate, kinetics studies could be employed so
that activation energy was obtained at any time during the reaction. Thermal analysis is an important approach
to study the mechanisms of kinetics for the conversion of biomass. Thermogravimetric analysis (TGA), and dif-
ferential thermal gravimetric analysis (DTGA) with the help of mass spectrometer is an analytical method was
extensively used to determine the pyrolysis characteristics decomposition behavior, and evolved gas elements of
a material (Hong et al., 2020).
• Zhongqing et al. (2015) investigated with palm kernel shell using TGA with inert gas atmosphere found that the
decomposition rate was slower than the other residues due to the high content of lignin. Hauhuu et al. (2015)
found the activation energy of the Spirulina Platensis, and Chlorella protothecoides as 76–97 kJ/mol and 42–52
kJ/mol, respectively.
Methodology
Microalgae biomass and characterization:

• Chlorella vulgaris is a species of chlorella and Spirulina Platensis is a family of Spirulina are
unicellular algae procured from Enviro Biotech, Coimbatore. The lipids from the species are
extracted using methanol as a solvent through chemical extraction method, and the residues
are washed in deionized water. The substrates were dried at 105 °C for 24 h to remove the
moisture, and it is stored in the air-tight plastic containers. The dried substrates were grained,
and sieved to obtain the uniform grain size less than 200 μm, and stored in a desiccator to
prevent the moisture.
• Algae used in this work is harvested at the same season to ensure a similar composition for
all trails. Hence the solid content in the algae was composed of cellulose, hemicellulose,
chlorophylls, polysaccharides, proteins and lipids, organic and inorganic compounds. The ele-
ment such as carbon, nitrogen, and hydrogen content was found using CHNS analyzer, and it
is presented in Table1. The ash content, and volatile solids were determined using ASTM
D2974-87 and ASTM E872-82, respectively. The repeatability, uncertainty and experiment con-
fidence level are presented in the following Table.
Microalgae biomass and characterization:
Thermochemical conversion of the dried microalgae:

• The pyrolysis of residue algae biomass was investigated by a TGA/ DTA TA Instruments Model
SDT Q600, coupled with Gas Chromatography and Mass Spectrometry to study the behavior
of weight loss, and gas formed during the pyrolysis process. A small quantity of SP and CV (5
g) is loaded in the copper crucible, and the high purity nitrogen is ramped at a flow rate of
100 milliliter/min in the pressure of 1 atm. For each experiment, the furnace was heated from
room temperature to 1100 °C with the different heating rates of 10, 20, 30, and 40 °C/min.
• By integrating the positive, and negative peaks of an endothermic and exothermic reactions,
combustion heat is calculated using the DSC curve. The evolved gases from the substrates
were determined using the thermo-gravimetric analyzer coupled with Fourier transform in-
frared spectroscopy (Perkin Elmer Pyris 1 TGA coupled with Clarus 600 T). 10 g of SP, and CV
samples were loaded in platinum crucible purged with helium gas at the rate of 40 ml/min us-
ing electron ionization of 70 ev. The samples were heated from the ambient temperature to
980 °C at 40 °C/min, and the evolved gas is determined through the peaks and signal
Iso-conversional kinetic modeling:
• As per the (Li et al., 2013; Hong et al., 2020; Fernandez et al., 2020) the kinetic analysis of any
substrates was described into three equations. The first stage determined the bio-char and gas,
and the second stage of equations represents the oxidative decomposition of residue algae,
which form gas and ash.

The combustion of algae is complex due to the presence of solid matter and combined effect
of adsorption, desorption, nucleation, and surface diffusion. The conversion of biomass into
volatile components can be determined as:

‘m0’ is the initial mass of the sample, ‘mt’ represents the mass at which time
t and ‘m∞’ is the final mass available in the crucible. The rate of the thermal
decomposition of the solid (dα/dt) can be evaluated in the functional
product of temperature and differential functional conversion, f(α) and k is
the reaction rate constant, which can be derived from Arrhenius equation.
Arrhenius equation:

Where, T is the absolute temperature.

By replacing the Arrhenius equation, the following temperature-dependent terms are shown in following
equation. A is the pre-exponential factor s−1 , E is the activation energy, kJ/ mol,
R is the gas constant, 8.314 J mol/K.

where (β = dT/dt) is the linear heating rate, and the activation energy of the
substrates was determined using Ozawa Flynn wall, which is shown below
(Kassim et al., 2014).

where, α = constant Activation energy ‘E’ was determined by plotting a

graph between ln (β) vs 1/T and by obtaining the slope drawn from the
straight line.
Results and Discussions
Proximate and ultimate analyses:
TGA analysis at different heating rates:

TGA analysis of different heating rates: (a) Chlorella vulgaris (b) Spirulina Plantensis
Pyrolysis behaviour (Thermo-gravimetric analysis - Nitrogen atmosphere) :
Differential scanning calorimetry (DSC):

DSC curves for the pyrolysis of (a) Chlorella vulgaris (b) Spirulina Platensis.
Oxidation Kinetics:
Oxidation Kinetics:
Thermo-Gravimetric Infra Red Characteristics:
Thermo-Gravimetric Infra Red Characteristics:

Apparent activation energy of (a) Chlorella vulgaris (b) Spirulina Platensis

Evolved gas analysis:

• In order to identify the prominent ions, the interface is run with a preliminary broad scan with m/z n the
range of 0–300 amu, detected ions, and atomic mass units were selected from the database of National Insti-
tutes of Standards and Technology (NIST).
• The molecular ions, and the portable parent molecule present in the biomass during pyrolysis. The major
ions detected in SP, and CV have masses 2, 17, 18, 27, 45, 58, and 64, corresponding to the hy-drogen,
amines, water, nitriles, acetic acid, amides, and sulfones, respectively. At temperatures < 160 °C evolution of
H2O, CO and CO2 is detected. Additionally, C6H6, C3H8N, CO2, CH4N, HCN, H2O, and CO are also formed due
to the moisture content in the biomass. The volatile compounds are C2H5, CH3+, CH4, and C2H2 released at
the temperature range of 160–450 °C.
• As per (Sanchez-Silva et al., 2013; Hong et al., 2020), the second stage was observed as main pyrolys-is stage
where all the proteins and carbohydrates are converted into amines due to the thermal de-terioration of the
proteins. In this region, the proteins are converted into nitrile and amines. Carbon-dioxide is also found,
probably due to breaking and rearranging the proteins and saccharides.
Conclusions
• In this research, de-oiled biomass such as Chlorella vulgaris (CV), and Spirulina Platensis (SP) was uti-
lized to study its kinetics of pyrolysis behavior. The pyrolysis conditions studied were set at the dif-
ferent heating rate at 10 °C, 20 °C, 30 °C and 40 °C/min under inert atmosphere in the temperature
range of 30–1000 °C. Iso-conversional method was adopted to calculate the apparent kinetic energy,
and it was found that the activation energy of the CV is in the range of 8.7–20.9 kJ/mol., which is
less than the SP range of 16.4–157.7 kJ/mol. The kinetics data reveals the CV is found suitable for
fuel production. The average regression coefficient value of the experiments was obtained as R 2 0.96.
The major products found were H2O, CO2, and CH4, which shows the potential for producing syngas,
and biofuel from the microalgae.
• In this research work, the thermal behavior of the two species CV and SP residues were studied. The
conversion of 0.2 to 0.8, the activation energy in both the case increased first and then decreased,
and the energy needed to activate the reaction of CV was 12.83 kJ/mol, which is lower than the SP
as 47.2 kJ/mol. Hence, it is concluded that the CV can be used for thermal conversion to extract the
carbon-dioxide, hydrogen, steam, amines, and nitriles using pyrolysis method. Further, the future
scope of work could be extended to the optimization of process variables on pyrolysis system.
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 Thank you
Suvranil Banerjee
suvranil.banerjee@gmail.com