Sustainable Chemistry and Pharmacy

Volume 33, June 2023, 101137

Optimization of process parameters to intensify the yield rate of

biodiesel derived from waste and inedible Carthamus lanatus (L.)
Boiss. seeds and examine the fuel properties with pre-heated
water emulsion
Mahesh Gurusamy a , Suresh Vellaiyan b , Muralidharan Kandasamy c, Yuvarajan Devarajan d

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Abstract

Second-generation biodiesels derived from non-edible feedstocks are a viable alternative to diesel, and the transformation of
Asteraceae seeds into biodiesel is the topic of some fascinating research. In the earlier experiments, no attempt was made to
optimize Carthamus lanatus (L.) biodiesel (CLB) for a higher yield rate and to discover whether it was suitable for use with a pre-
heated water emulsion. The current study aims to extract biodiesel from Carthamus lanatus (L.) Boiss. seeds under optimal
conditions, evaluate the effect of reaction parameters on yield rate and determine the appropriateness of pre-heated water-CLB
emulsion for fuel applications. The reaction parameters such as catalyst concentration (CC), methanol ratio (MR), impregnation
time (ITE) and impregnation temperature (ITP) were optimized using response surface methodology. The function group and
chemical constituents of CLB were assessed by Fourier-transform infrared (FTIR) spectroscopy, and Gas chromatography–mass
spectrometry (GC-MS). The CLB was blended with various volume concentrations of pre-heated water and their physicochemical
properties were assessed. With CC of 2.51737%, MR of 11.0135:1, ITP of 115.625 °C, and ITE of 140.292 min, the CLB yield rate is
intensified to 94.51%, and the ITE has a major influence (52%) on yield rate. The FTIR report indicates that the carbon-based
components are significantly contributed, and the GC-MS report states that linoleic acid has a maximum contribution.
Physicochemical properties reveal that CLB is a suitable alternative to diesel and that up to 15% of the pre-heated water contained
in CLB can be used as a direct fuel.

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Introduction

A significant amount of greenhouse gases released from fossil fuel combustion such as coal, oil, and gas cover the Earth and trap
solar radiation. Fossil fuels are accounted for more than 75% of greenhouse gas emissions and assume to be the biggest contributor
to climate change (Khalili et al., 2019). In order to prevent the worst consequences of climate change, emissions must be lowered by
half by 2030 and to null by 2050. To do this, nations should stop relying on fossil fuels and put resources into reliable, safe, scalable,
and economical renewable energy sources (Laimon et al., 2022). The sun, wind, waste, crops and seeds from the Earth are all
abundant sources of renewable energy that rebuild themselves naturally and emit little to no greenhouse gases and other air
pollutants (Basha et al., 2021). Out of these, biodiesel from vegetable seeds and crops has gained recognition as one of the most
potential renewable fuels due to its biocompatibility, durability, and involvement in lowering pollutant emissions (Ahmad et al.
2022).

According to the source, biodiesels are typically divided into three generations: first, second, and third. Edible biomass is closely
linked to first-generation biofuels, and lignocellulosic feedstocks and municipal solid wastes are used in the production of second-
generation biofuels. Vegetables and vegetable oil are the sources for the first generation of biodiesel production. First-generation
biodiesel frequently uses the following feedstocks: palm, coconut, cottonseed, sunflower, groundnut, and canola. However, the
edible food products used to develop first-generation biodiesels decreases the quantity of edible food available for human ingestion
and drive up the food costs in the market (Callegari et al., 2020; Go et al., 2021). The non-edible oils, crops, woods and husks are
under the umbrella of second-generation biodiesels. These resources essentially end our reliance on crops for the generation of oil.
Karanja, rubber seed, mahua indica, neem, jatropha, and garbage from businesses and residences are some of the sources of
second-generation biodiesels. It has been established that using these feedstocks to make second-generation biodiesel is more
effective and ecologically responsible than using fuel sources to make first-generation biodiesel (Nagappan et al., 2020). However,
the growth of non-edible crops for second-generation biodiesel demands a significant quantity of agricultural farmland, which
interferes with the area utilized for the production of edible crop production (Beig et al., 2021; Sivamurugan and Devarajan, 2018).
Inadequate feedstock output for industrialization and large upfront growth and installation expenses for economic viability is the
key hurdles in the development of third-generation Algae biodiesel, despite the fact that minimizes the food and land problems
associated with first and second-generation biodiesel (Saad et al., 2019).

Carthamus lanatus (L.) seeds (CLS) are proposed as a novel feedstock for the present study to produce second-generation biodiesel.

This plant is belonging to the Asteraceae family and can be found in India's topographical and biological regions. The seeds can be
spotted in nurseries, neglected regions along roads, meadows, and the lower mountain belt. The phytochemistry, pharmacology
and medicinal properties of Carthamus lanatus (L.) seeds were reported by Asgarpanah and Nastaran (2013). The fatty acid
composition of Carthamus lanatus (L.) oil was reported by Gecgel et al. (2007). According to the antioxidant and antimicrobial
properties of Carthamus lanatus (L.) oil reported by Khémiri et al. (2020), Safflower oil may be a suitable natural alternative
treatment for microbial infections. Fatty acid methyl esters' qualitative and quantitative analysis of Carthamus lanatus (L.) oil is
carried out by Gasimova (2019) who reported that the seed oil from CLB seeds has essential fatty acids which are having the
potential to use as a medicinal and technical plant. Munir et al. (2023) proposed the Carthamus lanatus (L.) biodiesel as a novel
feedstock for fuel application and reported its basic qualities. However, no studies have tried to chemically transform Carthamus
lanatus (L.) Boiss. seed oil into biodiesel at optimal conditions and improve its energy and environmental qualities through fuel

modifications.

A broad chemical technique called transesterification is frequently used to convert natural bio-oil to biodiesel. A mono-alkyl ester
is the major product of the transesterification reaction, which is typically carried out at high temperatures with a catalyst.
Triglycerides are transformed into monoglycerides by developing diglycerides (combing methanol and triglycerides),
monoglycerides (combining diglycerides and methanol), and glycerol (combining monoglyceride and methanol) (Kundu and De,
2021). The transesterification process, which depends on the reaction circumstances, is influenced by various aspects. If the
circumstances are not optimal, either the process fails or performs with much lower efficiency (Sharma et al., 2022). To produce
biodiesel that conforms to legal criteria with a high level of efficiency, each characteristic is therefore equally important. Free fatty
acid (FFA) content, moisture content, alcohol forms and molar ratios, catalytic forms and levels, reactivity duration and
temperature, and finished product detoxification are the most important variables that affect the transesterification reaction
(Elango et al., 2019). Hence, the optimization of transesterification process parameters is a needed effort to attain higher process
efficiency with economical value.

Various sources claim that the use of biodiesel in transportation applications significantly raises nitrogen oxide emissions while
significantly lowering hydrocarbon and carbon monoxide emissions. Hedayat et al. (2016) pointed out that In addition to reducing
the mass, the oxygen in the fuel also increases the reactivity of the emitted particulate matter. Oxygenated organic fraction is a
reactive component of PM and is directly associated with the oxygen concentration of the fuel. Using waste cooking oil and
triacetin, Zare et al. (2017) conducted an engine performance investigation under transient and steady-state operating
triacetin, Zare et al. (2017) conducted an engine performance investigation under transient and steady-state operating
circumstances and found that the oxygenated fuels had reduced indicated mean effective pressure (up to 18.7%), and brake mean
effective pressure (up to 21%) compared to diesel. Indicated torque, maximum in-cylinder pressure, and maximum rate of pressure
rise were all higher when oxygenated fuels were used in place of diesel during the transient modes of the custom test, but during
steady-state, most oxygenated fuels had lower values for all three metrics. Smaller blend percentages demonstrated a higher
reduction in particle emission than blend percentages of above 20%, according to research conducted by Rahman et al. (2015) on
the particle emissions from commercially farmed microalgae.

According to Saravanan et al. (2020), diesel fuel containing 20% rapeseed and mahua biodiesel reduces HC and CO emissions by
8.56% and 20.66%, respectively, while the NOx emission increases by roughly 4%. Selvan et al. (2022) noted that diesel fuel
containing 10% cotton seeds and 10% eucalyptus oils reduces the HC and CO emission by about 22% and 31%, respectively. The
majority of biodiesel derived from agricultural and industrial crops produces a large magnitude of NOx emission when compared
to regular diesel fuel, according to a thorough review of work conducted by Xue et al. (2011). Biodiesel with a high oxygen content
produces a high flame temperature, which accelerates the generation of NOx emissions. In addition to putting a strain on human
respiratory health, NOx emissions to the atmosphere also contribute to acid rain and ground-level ozone. Therefore, it is imperative
to make the necessary effort to commercialize biodiesel with low NOx emission.

Emulsifying water and biodiesel is an effective approach to reducing the overall emissions from an engine running on fuel. The
latent heat absorbed by water particles lowers the incidence of NOx formation and greatly lowers the combustion flame
temperature (El-Adawy et al., 2023). The micro-explosion and secondary atomization of water emulsion effectively boost the air-
fuel mixing rate, which also promotes effective and clean burning. According to Vellaiyan (2020a), who carried out the
experimental trial with the water-soybean biodiesel emulsion, adding 10% water to the biodiesel efficiently lowers the emissions of
HC, CO, and NOx by 19.1%, 22.6%, and 13.8%, and improves the engine performance by 13%. According to Maawa et al. (2020)
experimental's findings, adding 5% water to a diesel-biodiesel blend increases engine torque by 28.4% and lowers fuel consumption
by 7.3%. Even if a diesel-biodiesel blend with 30% water reduces NOx emissions by 26.17%, high water concentrations have a
substantial impact on other emission parameters and engine characteristics. According to several studies employing water in diesel
and diesel-biodiesel blends, the engine proves efficient combustion with a substantial reduction in emissions when the base fuel
contains up to 10% water (Sartomo et al., 2020). The present investigation is the result of continued advancement in emulsion fuel
techniques, which have been chosen to decrease dependence on carbon-based fuel and enhance the water content in the base fuel
with effective overall performance.

The presence of a surfactant in the biodiesel-water emulsion also affects the characteristics of the fuel, particularly its viscosity,
density, calorific value and flash point (Vigneswaran et al., 2021). The fuel injection system is impacted by a rise in fuel viscosity
and density brought on by the presence of surfactant. Another issue in the emulsion fuel arena is emulsion stability, where an
unstable emulsion can potentially affect the combustion system (Vellaiyan 2020b). To prevent harm to the injection and
combustion systems, a limited concentration of water is preferred for biodiesel based on the physicochemical properties variations
(Chen and Tao 2005). As the temperature of water rises, viscosity and adhesion strength typically drop as well, making
emulsification easier in general. The emulsions will deteriorate as a result of an abnormal temperature increase since it tends to
cause the particles to agglomerate. Increasing temperature has certain negative effects on the emulsifier's interfacial adsorption.
The emulsion will split from the surfactant that is weakly adsorbed on the oil-water interface. This will make collisions and
coalescence more likely, which will make water-in-oil emulsions unstable. From the discussion above, it is obvious that a small
increase in the emulsion phase (water) temperature significantly improves the emulsion stability and other physicochemical
parameters when a surfactant is used as the emulsifier for high-viscosity biodiesel emulsion. So, to improve energy and
environmental benefits, high-temperature water is introduced in the proposed investigation to increase the amount of water in
emulsion fuel.

Second-generation biodiesel from vegetable seeds and crops has become recognised as one of the most viable renewable fuels. The
conversion of seeds into biodiesel is the subject of some fascinating studies in the Asteraceae family. Carthamus lanatus (L.) Boiss.
seed oil, a highly unsaturated fatty acid seed would be reasonable feedstock for biodiesel production. The optimization of the
transesterification process parameters is necessary because the yield rate of biodiesel produced by the transesterification process
depends on the alcohol forms and molar ratios, catalytic forms and levels, reactivity duration and temperature, and finished
product detoxification. High oxygen content in biodiesel encourages the formation of NOx emissions, and water emulsion in the
base fuel is an impressive technique to suppress the NOx emission with improved combustion characteristics. Previous research
has shown that the base fuel with 10% water is the best combination and development in the emulsion fuel technique could
increase the water content in emulsion fuel, which will reduce the dependency on carbon-based fuels further. To the best of the
authors' knowledge, this study is the first to suggest ways to transform CLB into a productive and environmentally friendly energy
source. These suggestions include CLB production at optimal conditions, CLB fuel characterization towards fuel application, and the
suitability of CLB with pre-heated water emulsion.
In view of the aforementioned motivations, the CLB was extracted from CLS through the transesterification process and the
response surface methodology (RSM) was used to optimize the crucial transesterification parameters to achieve a higher biodiesel
yield rate. These parameters included the catalyst concentration (CC), the methanol ratio (MR), the impregnation time (ITE), and
the impregnation temperature (ITP). To analyse the characteristics of CLB, Fourier-transform infrared (FTIR) spectra and gas
chromatography–mass spectrometry was utilized to identify the CLB's chemical contents (GC-MS). The alterations that occurred in
the CLB's physicochemical properties when it was blended with pre-heated water at a temperature of 50 °C at varying volume
concentrations, such as 5%, 10%, 15%, and 20%, were measured, and the appropriate amount of pre-heated water in CLB was
recommended to the engine application.

Section snippets

Preparation of CLB

Seeds of Carthamus lanatus (L.) were collected from the local supplier and the moisture content in the seed was removed by drying
the seeds under normal sunlight for about two days. The seeds are around 6 mm in length, have a uniform grey-brown colour, and
are ribbed with a smooth outer shell. The substances needed for the oil extraction and transesterification, including n-hexane
(C16H14), methanol (CH3OH) and sodium hydroxide (NaOH), were procured in our laboratory. The solvent extraction…

CLB yield rate estimation based on the Box-Behnken design matrix

Design Expert 13's Box-Behnken design matrix was used to set the reaction parameters, and Table 1 shows the predicted and
experimental values of biodiesel yield rate (YRB) for the associated reaction parameter combinations. It is noted that the
experimental values are in good agreement with predicted values. According to the experimental data, Run No. 16 (CC 2.5%, MR 14,
ITP 105 °C, and ITE 180 min) promotes a high biodiesel yield rate in comparison to other trials, whereas Run No. 25 (CC 1.5%, …

Prospects for future research

The current research attempts to improve the yield rate of CLB by optimizing the process conditions and characterizing the fuel's
properties. Fuel qualities were assessed and compared to ASTM requirements to verify the appropriateness for diesel fuel
replacement when CLB was added to water at 5%, 10%, 15%, and 20% volume concentrations. Fundamental combustion,
performance, and emission evaluation of CLB performed in a diesel engine to understand the emergence of energy and
environmental…

Conclusion

The current study is the first to describe the optimization process used to intensify the yield rate of biodiesel from Carthamus
lanatus (L.) Boiss. seeds and explores the impact on physicochemical characteristics while the different volume concentrations of

pre-heated water were blended with biodiesel. Key reaction parameters like CC, MR, ITE, and ITP were optimized, and it was shown
how these affected YRB in more precision. The FTIR spectra of the CLB were used to examine its qualities, and…

Ethical approval

NA.…

Funding

The author declares that there was no funding received to carry out this work.…

Credit author statement

Mahesh Gurusamy and Suresh Vellaiyan equally contributed to experimental data collection, optimization, methodology,
interpretation of the results and manuscript preparation. Muralidharan Kandasamy and Yuvarajan Devarajan contributed to
validating the data and report drafting.
All authors have read and agreed with the submitted version of the manuscript.

The authors declare that the submitted work is original and not have been published elsewhere in any form or language (partially
or in full).…

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.…

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References (41)

B. Beig et al.
Current challenges and innovative developments in pretreatment of lignocellulosic residues for biofuel production: a
review
Fuel (2021)

G. Chen et al.
An experimental study of stability of oil–water emulsion
Fuel Process. Technol. (2005)

M. El-Adawy et al.
Unveiling the status of emulsified water-in-diesel and nanoparticles on diesel engine attributes
Case Stud. Therm. Eng. (2023)

R.K. Elango et al.

Transesterification of castor oil for biodiesel production: process optimization and characterization
Microchem. J. (2019)

F. Hedayat et al.
Influence of oxygen content of the certain types of biodiesels on particulate oxidative potential
Sci. Total Environ. (2016)

N. Kumar et al.
Production, characterization and utilization of second generation biodiesel blend in diesel engine using water and
nanoparticles as additives
Fuel (2022)

M. Laimon et al.
System dynamics modelling to assess the impact of renewable energy systems and energy efficiency on the
performance of the energy sector
Renew. Energy (2022)

W.N. Maawa et al.

Performance, combustion, and emission characteristics of a CI engine fueled with emulsified diesel-biodiesel blends
at different water contents
Fuel (2020)

M. Munir et al.
Cleaner production of biodiesel from novel non-edible seed oil (Carthamus lanatus L.) via highly reactive and
recyclable green nano CoWO3@ rGO composite in context of green energy adaptation
Fuel (2023)

S. Ramalingam et al.
Effect of Moringa oleifera biodiesel–diesel–carbon black water emulsion blends in diesel engine characteristics
 Effect of Moringa oleifera biodiesel–diesel–carbon black water emulsion blends in diesel engine characteristics
Energy Rep. (2022)

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