Biofuels

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Production of biofuels from fish wastes: an

overview

D. Yuvaraj, B. Bharathiraja, J. Rithika, S. Dhanasree, V. Ezhilarasi, A. Lavanya

& R. Praveenkumar

To cite this article: D. Yuvaraj, B. Bharathiraja, J. Rithika, S. Dhanasree, V. Ezhilarasi, A. Lavanya

& R. Praveenkumar (2016): Production of biofuels from fish wastes: an overview, Biofuels, DOI:
10.1080/17597269.2016.1231951

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BIOFUELS, 2016
http://dx.doi.org/10.1080/17597269.2016.1231951

Production of biofuels from fish wastes: an overview

D. Yuvaraj a, B. Bharathirajaa, J. Rithika a
, S. Dhanasree a
, V. Ezhilarasi a
, A. Lavanya a
and
R. Praveenkumarb
a
Vel Tech High Tech Dr Rangarajan Dr Sakunthala Engg college, Avadi, Chennai; bArunai Engineering college, Tiruvannamalai

ABSTRACT ARTICLE HISTORY

Every year billions of tons of fish waste are produced by fish processing units. These wastes Received 22 August 2015
when dumped into the environment cause emissions which in turn degrade the land. An Accepted 24 August 2016
alternative solution for the problem involves their processing into biofuel, pharmacological KEYWORDS
components, fertilizer and fodder. Biofuel is a trending concept and an alternative for present Fish waste; biofuel; non-toxic;
day fuels. Biofuels are pollution free and thus are advantageous over current fuels. Biofuels are transesterification; anaerobic
produced from organic waste, seaweed, and micro-algae. The current research on fish wastes digestion
for the production of biodiesel is mainly because of their nontoxic and biodegradable nature.
Biodiesel produces less air toxins, CO2, hydrocarbons and other particulates when compared to
the standard fuel or diesel. The conversion process involves extraction of fish oil from the waste
of the fishing industry. The oil is cleaned and purified. With the addition of a catalyst, biodiesel
and bio-gas are produced by transesterification and anaerobic digestion respectively. Various
results such as Fourier transform nuclear magnetic resonance (FT-NMR), gas chromatography
mass spectrometry (GCMS) and proton nuclear magnetic resonance (H-NMR) analysis, and best
management practices (BMP) assay show the efficient conversion and working of biofuels.

Introduction materials such as vegetable wastes and plants is not

practical. Planting and cultivation assets are unfavor-
The world is at the edge of an energy crisis, where
able [5]; obtaining biofuel from waste materials yields
India suffers badly due to a hike in energy prices and
oil which can then be processed to yield biodiesel, but
consumption. The standard fuels used presently such
its physical and chemical characteristics do not match
as petroleum and diesel are from non-renewable sour-
that of the currently used fuel and are not acceptable
ces such as fossil fuels. The rich reserves of fossil fuels
to current engines (Tables 1 and 2). [5]. When oil is
are present in the Arabian Peninsula and are depleting
obtained from an edible source this is a waste of food;
slowly. These fuels on combustion emit toxic elements
a main disadvantage in producing fuel from vegetable
into the environment that causes effects such as air
oil [15].
pollution and health ailments. The main pollutants
The fish industry is one of the world’s largest indus-
emitted include CO2, oxides of nitrogen, and sulfur
tries where tons of fish are used daily. India is the sec-
dioxide. Due to their ill effects and their non-degrad-
ond largest producer of fish with 5.43% of the global
able nature a new technology is emerging to compen-
production [16]. Fish production during 2009–10 was
sate the need for fuel energy: the concept of biofuel. In
found to be 78.51 lakh tones. Every year a billion tons
India the biofuel concept is an emerging alternative
of fish are utilized for edible purpose; waste non-edible
form, whereas developed countries such as UK [1], Iran
parts include head, viscera, dorsal fins, tail, skin, and
[2], and Greenland [3] have already implemented this
liver. These waste non-edible parts are considered to
technology. Many basic works are ongoing for the
be worthless garbage and discarded without any
implementation of this technology in India. Biodiesels
recovery of valuable products by dumping on land or
have a higher flash point [2] (minimum 164
C) than
hauling into the ocean [17]. India generates 2 million
regular diesel (minimum 52
C), are nontoxic and are
metric tonnes of by-products due to fish processing
fully biodegradable [4]. They reduce the air toxins, CO2,
[16]. The organic compounds present in the wastes
hydrocarbons and other particulate matter (PM) when
have high biological oxygen demand which when not
compared to standard fuel or diesel. Thus they are the
managed properly pose adverse environmental effects
most suitable form of energy source [4]. Biofuels can
such as generation of toxic hydrogen sulfide gas,
be obtained from organic wastes (including vegetable
increased gathering of scavengers in discharge loca-
wastes [5–7], animal wastes [8–10], and fish wastes
tions, and noxious conditions caused by odors, bacteria
[11,12]), micro-algae [13], seaweeds and plants such as
and waste decomposition [18]. The most important
Jatropha sp. [14]. The extraction of biofuel from plant

CONTACT B. Bharathiraja drbharathiraja15@rediffmail.com

© 2016 Informa UK Limited, trading as Taylor & Francis Group
2 D. YUVARAJ ET AL.
environment-friendly and profitable option for utiliza-
tion of fish waste includes animal feed supplements,
aquaculture feed, fishmeal and fish silage, renewable
energy in the form of biodiesel and biogas [10,19],
composting for production of organic fertilizers, extrac-
tion of natural pigments, extraction of novel and indus-
trial enzymes like proteases [20,21], cosmetics,
pharmaceutical industries such as collagen, fish protein
hydrolysate, fish bone extracts, and polyunsaturated
fatty acids [16,22–24]. In this paper we review the proc-
essing and extraction methodologies of biofuels, purifi-
cation, and their efficiency.
Processing
During the processing of fish wastes some conditions
are considered. The wastes of fish rich in Omega-3-
fatty acids are unavailable, since this compound is
essential for the pharmaceutical industries. Fish that
are very dry are also avoided. The biofuels obtained
from the wastes include two important classes: biodie-
sel and bio-gas(bio-methane).
Biodiesel production
Biodiesel can be extracted using various methods such
as: microwave assisted-lipid extraction [25], trans-
esterification [23,26,27], single step transesterification
using alkaline catalyst [28], two stage reaction process
[29], separation process [30] and conventional pro-
cesses including wet rendering and dry rendering [31].
Transesterification
Transesterification is the basic step that yields biofuel
products. The step prior to the transesterification is fish
oil production. Fish oil is produced by means of
machinery. Fish wastes are fed into a cooker at 100
C
from where it is moved to the expeller. This expeller
separates the biomass from the liquid. Here, the liquid
is squeezed out and solid biomass remains in the
expeller. The liquid that comes out is estimated to
have 54% water, 4% solids and 42% oil. The liquid
moves to pre-clarification where it separates into three
layers: oil, liquid, and biomass. Sometimes the oil is
obtained from the mechanical expeller and followed
by solvent extraction (using n-Hexane). Thus, the fish
oil is alone removed for the further transesterification
process.
Fish oil is used for transesterification without any
further treatment. Although the stoichiometric ratio for
transesterification reaction is 3:1 alcohol to oil molar
ratio, experiments have shown that a molar ratio rang-
ing from 6:1 to 12:1 would result in the most optimal
transesterification of triglycerides into FAME [28]. Using
a homogenous catalyst, it has been observed that 1
wt.% of catalyst is optimal for the transesterification of
triglycerides [28]. Practically, 25 ml of waste fish oil is
mixed with 1 wt.% of catalyst (CH3ONa). Based on ear-
lier work using frying oil, 40 vol.% of methanol was
considered an optimum amount for transesterification
[24]. During optimization, the same volume ratio of
methanol to oil was found to be optimum to obtain
maximum yield of biodiesel from waste fish oil (data
not shown).
Therefore, 40 vol.% of methanol (i.e. 10 ml) was
added to the feedstock and the contents were heated
and stirred (1000 rpm) simultaneously at 60
C for
1 hour. The products were kept in a separating funnel
and a clear separation of biodiesel and glycerol was
observed. The estimation of conversion of oil to FAME
was calculated using Fourier transform-nuclear mag-
netic resonance (FT-NMR) through the following equa-
tion as previously described by Knothe:
C D 100£ð2AME =3Aa ¡ CH2 Þ (1)
where C is the conversion of feedstock to FAME, AME is
the integration value of the protons of the methyl
esters (the strong singlet peak), and Aa-CH2 is the inte-
gration value of the methylene protons.
The yield of biodiesel was determined by weighing
the biodiesel obtained after transesterification. The bio-
diesel yield (%) was calculated on the basis of the ratio
of weight of the biodiesel to the weight of fish oil (ini-
tially taken for experimentation) multiplied by 100. Bio-
diesel fuel was produced from the fish oil after the
chemical reaction (transesterification reaction between
methanol, potassium hydroxide and oil from fish waste).
For each liter of oil, 0.9 l biodiesel was produced
(Figure 1). Biodiesel is typically produced through the
reaction of fish oil with methanol in the presence of cat-
alyst to yield glycerins and methyl esters. This process
for making biodiesel is relatively simple. The process is
known as transesterification. The step by step mecha-
nism of this reaction is shown in Figure 2. The process
of biodiesel production from waste fish oil is indicated
in Figure 3. In the first step, the processed waste fish oil
is fed into the system. The existing water in the reaction
at higher temperature levels resulted in triglyceride
hydrolysis and free fatty acid formation. Free fatty acids
neutralized the catalyst and led to soap formation.
Therefore, it can be implied that the existence of water
Figure 1. Fuel prices across the globe.

Figure 2. World capture fisheries and aquaculture production.
and free fatty acids caused soap production. For per-
forming the tests, the catalyst of potassium hydroxide
(1%oil weight) and alcohol to oil volumetric ratio
of1:4wasapplied.Since waste oil was used for biodiesel
production, the color of the resulting mixture was dark
brown during the early stages of reaction turning to a
lighter color at the later phases of the reaction. The
reaction was conducted for 2h at a temperature of
60
C, agitation speed of 300 rpm and at ambient pres-
sure.The reason for selecting the temperature value of
60
C was that the temperature of reaction had to be
below the boiling temperature of the ethanol (64
C).
The biodiesel produced contains no sulfured PM that
Figure 3. The process flowchart of biofuel production from fish wastes (courtesy ENERFISH Vietnam).
BIOFUELS 3
contributes to air pollution. Sulphur and PM has been
responsible for black smoke and problems commonly
attributed to soured or dirty diesel fuel. Biodiesel has
greater lubrications than petroleum diesel. After produc-
tion of the biodiesel, some standard specifications were
measured. It was noticed that these specifications are
matched with international standards (ASTM).
Microwave assistedlipid extraction method
In this method, the fish wastes were dried in a solar air
heater (55–60
C) and ground to fine powder. Lipid
extraction involves both the conventional solvent
method and the microwave assisted lipid extraction
4 D. YUVARAJ ET AL.
method. In the conventional method, solvents such as
chloroform, methanol and distilled water were used in
the ratio 1:2:0.8 and mixed with the biomass for
24 hours. The microwaveassisted lipid extraction was
done for 10 min at 80
C. The lipid was separated from
solvent by filtration and concentrated using a rotary
evaporator. For the efficiency of extraction, the total
crude lipid content can be estimated by % dry cell
weight. This was continued by the microwaveassisted
transesterification for the conversion of obtained crude
fish lipids to fatty acid methyl esters [32]. Some condi-
tions provided include: 6:1 methanol to lipid ratio at
65
C for 10min in the presence of 1.5 wt.% KOH cata-
lysts with magnetic stirrer bar which allows continuous
stirring. The acquired biodiesel is separated from glyc-
erol by centrifugation.
Two-stage reaction process
Fish wastes are collected, washed and allowed to boil
with water as a solvent. After boiling, the oil can be col-
lected from the solvent by separating funnel. The
obtained oil is taken further for the acid and alkali
esterification process to yield biodiesel. The acidesteri-
fication process is carried out using H2SO4 acid catalyst
in a three-neck flask. The fish waste oil was added with
methanol at the oil to methanol molar ratio 1:6 then
added with 2% H2SO4 acid catalysts. After esterifica-
tion, the liquid separates into two layers when sus-
pended in a separating funnel: oil (top layer) and a
liquid layer. This is followed by alkaline esterification
where the resulted oil is again taken in a three-neck
flask. The 2% NaOH solution was dissolved in methanol
and mixed with the oil. The oil, methanol, and NaOH
was transesterified for 60min. After the respective tim-
ings, the product was obtained in two layers where
biodiesel settles at the top and the glycerol at the bot-
tom. Then it is purified by adding distilled water and
shaking for 5min. The biodiesel is kept at 90
C in an
oven to remove the moisture.
Conventional methods
Wet rendering process
The wet rendering process involves the usage of raw
materials with relatively high oil content. The processes
involved include cooking, de-watering, separating and
purification.
Cooking
The cooking of fish to aid in the recovery of water
and oil is the first step in the conventional fish reduc-
tion plant. The fish cookers are of two types such as
Direct and Indirect cookers. The Direct cookers involve
the charging of fish in a hopper above the internal
screw conveyer. Steam is introduced through a series
of small inlet pipes into the lower part of the cooker.
The steam requirements for direct cooking are rather
high. Assuming a specific heat of 1 Btu per/lb CF for
fish and input temperature of 15.5
C (60
F) it would
require 270,000 Btu or approximately 300 lb of steam
to bring a ton of fish to 90
C (195
F). The cooked fish
are discharged through a short choke screw.
De-watering
Cooked fish is de-watered with the aid of a horizon-
tal bowl centrifuge. Cooked fish are passed through a
disintegrator in order to reduce them to pumpable
slurry. The slurry is pumped to the centrifuge, and clari-
fied pressed liquor and solids are recovered. Although
not generally used, the method is workable and gener-
ally recovers slightly more oil than a conventional
press. This process also leaves approximately 10%
more water with the solids.
Separating
The pressed liquor normally contains considerable
amounts of solid particles such as proteins, bone frag-
ments, and scales that are extruded by small openings.
These are generally removed by screening and
centrifuging. After the preliminary screening the feed
is fed into the disc bowl centrifuge. The solids recov-
ered are higher in oil than regular press cake and are
usually fed back through the presses, pressed sepa-
rately, or added to press cake and dried. After removal
of the suspended solids, the press liquor is ready for
separation. The liquid to be separated rises through
channels in the disc set. The position of the rising chan-
nels is determined by the proportion of the liquid
phases to each other. The light liquid phase (i.e. oil)
passes to the inside of the head of the bowl and is dis-
charged through a special section of the hood. The sol-
ids, together with a quantity of the heavy liquid phase,
are continuously discharged through the nozzles.
Purification
The older settling tank method of separating oil
press liquor allowed long contact time between oil,
water, and meal which allowed oxidation and degrada-
tion of the oil. Modern centrifuges produce a high
quality of oil as the oil separation takes place immedi-
ately after the separating process. This also increases
the yield by several gallons. A final polishing is required
to remove the moisture in the resultant oil. A typical
analysis of sardine oil that has been finished by a com-
mercial system is as follows:
 Moisture and volatiles0.11%
 Insoluble impurities0.01%
 Free fatty acid (as oleic) 0.45%
Dry rendering process
This is employed primarily for raw material which is
both relatively low in oil content and available in rela-
tively small quantities. The process is always a batch
process which involves a combined cooking and dry-
ing process. The material to be rendered, often a whole
fish, is processed in a rotary-type cooker-drier, with
drying occurring under vacuum. The dried meal which
at this stage contains the oil then goes to a batch type
hydraulic press which removes most of the oil. The

recovered oil is generally much darker in color than oil
rendered by the usual wet rendering method. The
usual alkali refining and clay-bleaching methods yield
an oil of acceptable color.
Separating process
In this process, the fish wastes are collected and cut
into small fragments. They are put in boiling water for
20 min and are cooled for 40min. The stewis strained
in a sieve with fast flow rate and again strained in a
fine sieve. This process is repeated 2–3 times and the
resulting filtrate is suspended in a separating funnel to
separate the oil from waste water. This oil is subjected
to transesterification by ethyl route at a temperature of
60
C for 90min. The catalyst used here is potassium
hydroxide.
Biogas production
The main method for the production of biodiesel will
be transesterification but the methods for producing
different by-product along with the biodiesel will be
different. The above process is based on obtaining
glycerin, heat and electricity as the by-product. If a by-
product like biogas is to be produced, then anaerobic
digestion should be carried out between the process
steps. Oil-free fish waste (cake) can be used in biogas
production. Manure and sewage sludge could be uti-
lized together with fish waste. The digestate can be
used as fertilizer.
Anaerobic digestion
Anaerobic digestion is a collection of processes by
which micro-organisms breakdown biodegradable
materials in the absence of air. Some micro-organism
has been used for this process like Acetogensand
Methanogens which convert the organic acid into
methane. The final products from anaerobic digestion
are digestate including a variety of nutrients, and bio-
gas containing CH4 (50–75%), CO2 (25–45%) and by-
products such as H2S (<1%) (Table 1) [33]. The decom-
position process comprises four steps as follows:
Hydrolysis step.Here enzymes are involved that
convert larger molecules of polysaccharides into small
monomers, which makes their digestion easier for bac-
teria. The enzymes involved in the hydrolysis are
mainly amylases, lipases, proteases, cellulases, and
hemi-cellulases. The time required for the hydrolysis
step depends on the substrate: the hydrolysis of
Table 1. Composition of biogas produced from fish wastes.
COMPOUNDS VOLUME %
Methane 50–75
Carbon dioxide 25–50
Nitrogen <7
Oxygen <2
H2S <1
Ammonia <1
BIOFUELS 5
carbohydrates takes hours, while the hydrolysis of pro-
tein and lipids requires days.
Acidogenesis step. In this acid forming phase, the
soluble monomers are further broken down by volatile
fatty acids. In this step, some enzymes are produced
that hydrolyze the remaining complex parts of hydroly-
sis step.
Acetogenesis step. Volatile fatty acids are con-
verted into acetic acid, carbon dioxide, and hydrogen,
by using acetogens.
Methanogenesis step. Methanogenic bacteria con-
vert the products of Acetogenesis into methane and
CO2. These bacteria are the most sensitive to the oper-
ation conditions (pH, residence time, temperature).
The methane (by-product) is used as a biogas. This
technique is also a more profitable one because these
gases are in demand in order to replace Liquefied
Petroleum Gas.
Digestion by this process involves different types of
bacteria according to the temperature in the digester:
 Psychrophilic bacteria at low temperatures (10–
20
C)
 Mesophilic bacteria at normal temperatures (20–
35
C)
 Thermophilic bacteria at high temperatures (50–
60
C)
Different reactors have been used for different fish
waste for the production of the biogas.
Co-digestion
Anaerobic digestion of biomass is a commonly used
process utilizing troublesome waste for producing bio-
gas. Anaerobic digestion of fish wastes is also possible
but is currently not much used. Fish wastes have great
potential as a source of high valued organic carbon for
methane production but also have limitations such as
high content of ammonia and nitrogen. The anaerobic
treatments of fish wastes are possible with co-diges-
tion. Co-digestion involves the mixing of the fish
wastes with sludge mostly or other wastes, so that bio-
gas can be obtained efficiently. The main issue
involved in co-digestion is the balancing of various
parameters such as macro and micro nutrients, C:N
ratio, pH, toxic compounds and dry matter. The
method is carried out in mesophilic temperature using
Automatic Methane Potential Test System (AMTPS II).
This equipment automatically measures methane pro-
duction from batch test.
Conclusion
The single step transesterification using alkaline cata-
lyst (CH3ONa) performed in the study showed that
waste fish oil is low in acid value and could be used to
produce biodiesel of high FAME content. India has a
vast coastal area with a colossal consumption of fish.
6 D. YUVARAJ ET AL.
Table 2. Process parameters and products of biogas from fish wastes.
However, in the present scenario, since the fish mar-
kets are scattered all over the country, the waste parts
are usually disposed of as solid waste with no proper
application. These wastes could be channelized into
local biodiesel plants as an economic feedstock for
high-quality biodiesel production. Large scale projects
like the ones mentioned have been running quite suc-
cessfully throughout the world particularly in develop-
ing countries. The process to extract the fish oil from
the raw left over materials and then converting that oil
to biodiesel is energy intensive, however, some of the
biodiesel produced can be used to run the machinery.
This would make the process self-sustainable and
totally greenhouse gas emission free. Fishing ports
could set up cooperatives to collect fish waste and pro-
duce fish oil, fishmeal and biodiesel. This would mean
the construction of only one big plant instead of many
smaller ones; reducing costs and increasing quantity
and potential (Table 2).
Disclosure statement
No potential conflict of interest was reported by the authors.
ORCID
D. Yuvaraj http://orcid.org/0000-0001-7579-4157
J. Rithika http://orcid.org/0000-0002-6640-5727
S. Dhanasree http://orcid.org/0000-0002-5484-5274
V. Ezhilarasi http://orcid.org/0000-0003-4614-6825
A. Lavanya http://orcid.org/0000-0002-3161-326X
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