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Biodiesel Making from Waste Vegetable Oils: A Case Study of Lab to Plant
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Journal of Agricultural Engineering Vol. 47(2): January-March, 2010

Biodiesel Making from Waste Vegetable Oils: A Case Study of

Lab to Plant Technology Transfer
N.G. Shah1, Shoyeb Khan1 and S.M.Mahajani2

Abstract

Great deals of efforts are being made to promote bio-diesel as an environment-friendly alternative to the petro-
diesel to meet the increasing demands. Two important issues which are hindering the dissemination of the technology
are: raw material availability at an affordable cost, and the acceptable quality of the bio-diesel satisfying the BIS
standards. The study was undertaken with the duel objectives to make bio-diesel from cheaper unconventional raw
materials, as well as to demonstrate a process at a pilot plant scale at users’ site. Wastes of vegetable oil refining
such as acid oil as well as waste cooking oils were processed for making biodiesel. Process reported here used
esterification, followed by transesterification of oil using methanol, and a chosen catalyst. The processes were
initially studied on laboratory scale conversion units (20 l/batch), which enabled to determine the process parameters
for the pilot field-unit (400 l/batch). The process flow design, mass balance, process time for the batch processes
were established and are reported along with the important fuel properties of biodiesel such as density, viscosity,
moisture content and flash point. The technology has been demonstrated for its technical performance at a Village
Industry Centre, where the bio-diesel produced is used in-situ for electricity generation.

Some of the major energy issues in modern times for which
clear solutions become available will remain a challenge
to the scientific community are: global warming, depleting
fossil fuels, rising fuel prices and environmental pollution.
Renewable alternatives can help resolve the issues to some
extent. Biodiesel has caught attention of many because of
the relative simplicity in production and its possible use in
a decentralized manner. Biodiesel is becoming increasingly
popular as blends with, or alternatives to, petro-diesel.
India’s bio-fuel policy is expected to replace at least 5 % of
conventional fuel usage with bio-fuels by 2012, climbing
to 10 % usage by 2017 and by 20 % beyond 2017 (Shah,
2007). Production and use of bio-diesel on a larger scale,
not particularly in large size plants but large number of
plants distributed all over the country, will not only help in
decreasing the dependence on crude-oil imports but can
also help promote agriculture in marginal lands, economic
development of rural areas and sustaining good
environment.
In technical literature, biodiesel is known as fatty acid
methyl ester (FAME) produced from esterification of fatty
acids or transesterification of triglycerides using methanol.
FAME is commonly produced by transesterification process
using potassium hydroxide (KOH) or sodium hydroxide
(NaOH) as catalyst in methanol. It has high
biodegradability, and has low sulphur oxides (SOx) and
particulate emissions when combusted in diesel engines
(Graboski and McCormick,1998; Schuchardt et al.,1998).
Different vegetable oils are used in various countries for
biodiesel production (Coello et al., 2009; Rai and Sarnail,
2009). United States is an exporter of edible oils, and hence
it uses soybean oil as a raw material for biodiesel
production. Rapeseed oil is in use in European countries
for biodiesel production whereas tropical countries like
Malaysia use coconut or palm oil for this purpose
(Demirbas, 2006; Adholeya and Dadhich, 2008). India,
however is a net importer of edible oil, and hence the
emphasis is on non edible oils from jathropha, pongamia,
neem, mahua, simarouba (Sharma and Singh, 2008). Out
of these plants, jatropha and pongamia have shown promise
for biodiesel production (Meher et al., 2005). However, it
will take some time to grow these plants on large scale so
that the oil is available at a competitive price for biodiesel
production. The high cost of the vegetable oils, which could
be up to 75% of the total manufacturing cost, has led to the
production costs of biodiesel to exceed that of petro-diesel
(Phan and Phan, 2008). Adholeya and Dhadich (2008)
have compiled information on production and land policy
issues in technology of biodiesel making. After detailed
analysis of both raw material production and conversion
technologies, they concluded that biodiesel is an emerging
alternative and needs the desired attention for its

1
Centre for Technology Alternatives for Rural Areas, IIT-Bombay, Mumbai 400 076, (Email: nshah@iitb.ac.in); 2Department of Chemical
Engineering, IIT-Bombay, Mumbai 400 076
36
N.G. Shah, Shoyeb Khan and S.M.Mahajani
popularization. Their report to the Ministry of Rural
Development (MORD) also refers to the National Biodiesel
Mission that advocates active interaction of state and central
government ministries with the various organizations
involved in R&D as well as production linking the processes
to the grass root levels i.e. farmers to the end users. Bockey
(2007) reported that Europe represents 80 % of global
biodiesel consumption and production, and Brazil is
expected to surpass Europe and USA in biodiesel
production by 2015. The absence of a clear governmental
policy in India has inhibited several manufacturers from
entering biodiesel markets and there have been sporadic
instances of manufacturers importing palm oil to produce
bio-diesel (Marketresearch.com, 2008).
The motivation of this study was to test waste oils such as
acid oils and used cooking oils which are available in India
at about Rs 20-22 /l or less. Acid oil is a by-product of
vegetable oil refining, and has high amount of free fatty
acid (FFA) along with some triglyceride content in it. The
high acidity of this material does not allow the use of the
conventional one-step process of alkaline catalysis, because
of the formation of soap that causes problems in the steps
of washing and purification of biodiesel, thereby reducing
the overall yield.
MATERIALS AND METHODS
In this study, biodiesel was made on a laboratory scale at
20 l/batch and in field unit up to 400 l/batch. While the
acid-oils were procured from nearby edible oil making units
(Ruchi-Soya Ltd.), the used cooking oils were procured
from the nearby McDonald outlets. The other reagents such
as methanol, sulphuric acid and potassium hydroxide of
commercial grades were procured from the local chemical
market. Three batch processes were carried out to make
biodiesel from acid oil and identified waste cooking oil.
The process flow design, mass balances, and the batch
scheduling were studied. Standard laboratory methods were
used to characterize the biodiesel made in the pilot plant
for density, viscosity, flash point and moisture content
(Srinivas, 2009). The product was used in-situ in diesel
generators used for electricity generation at site.
Biodiesel Conversion Processes
Three different batch processes, as described in Figs.1a –
1c, were carried out to produce biodiesel from acid oil.
The processes were: (1) One-step sulphuric acid (H2SO4)
esterification, which involved use of a homogenous acid
catalyst (i.e. H2SO4), and vacuum distillation; (2) One-step
PTSA (para-toluene sulphonic acid) esterification process,
characterized by a homogenous PTSA acid catalyst and
37
JAE : 47 (2)
vacuum distillation; (3) Two-step PTSA-KOH process,
characterized by a homogenous acid (PTSA), alkaline
catalyst (KOH) and vacuum distillation.
Acid oils have FFA content of 75-80 per cent. Therefore
FFA was first converted to esters in a pre-treatment process
using an acid catalyst to reduce the FFA content levels below
0.5% (Van Gerpen et al., 2004). The conversion of FFA to
FAME was estimated by taking samples and by estimating
the unconverted FFA by using following equation:
⎡⎛ 0.25 x ml of NaOH used ⎞ 282 .47 ⎤
% FFA = ⎢⎜ ⎟ ⎥ x 100 ... (1)
⎣⎝ 1000 ⎠ g of sample (i.e. 0.5 g) ⎦
Esterification was performed at 65oC. The pressure in the
reactors was slightly above the atmospheric pressure.
FAME was recovered by vacuum distillation at 750 mm of
Hg. The transesterification reaction was carried out at a
temperature of 60oC. The other reaction conditions were
same as used for the esterification process. Each process
alternative for acid oil as a raw material is described below.
Important steps in PROCESS-I (Fig.1a) were: (i) addition
of sulphuric acid catalyst to the raw material, (ii) cooking
of reaction mixture for about 1.5-2 h to perform
esterification, (iii) separation of acidic methanol layer, and
(iv) vacuum distillation of the esterified layer to produce
FAME. The first process required an additional step, which
was the neutralization of H2SO4 present in the methanol by
calcium oxide (CaO). The conversion using this process
was 75 to 80 per cent. The 20-25% residual oil that was
left in the reboiler after vacuum distillation was collected
and stored, which may be used as a raw material for soap
making process.
Important steps in PROCESS-II (Fig.1b) were: (i) adding
para-toluene sulphonic acid (PTSA) catalyst, (ii) cooking
of reaction mixture for about 2-2.5 h to perform
esterification, (iii) separation of acidic methanol layer, and
(iv) vacuum distillation of the esterified layer to produce
FAME. In PROCESS-II, the neutralization of acidic
methanol using CaO was eliminated. This is because PTSA
is not very corrosive, and stainless steel may be used for a
mixture containing PTSA. The yields from PROCESS-I
and PROCESS-II were comparable. Like in process-1, the
20-25% residual oil that was left in the reboiler after vacuum
distillation can be used as a raw material for soap making
process.
PROCESS-III (Fig.1c) involved two reactions, and the
important steps were (i) esterification reaction, (ii)
separation of acidic methanol layer, (iii) vacuum distillation
April-June, 2010 Biodiesel Making from Waste Vegetable Oils: A Case Study of Lab to Plant Technology Transfer

Fig. 1(a): H2SO4 esterification process (PROCESS-I)

Fig.1(b): One step PTSA esterification process (PROCESS II)

Fig.1(c): Two step PTSA-KOH process, characterized by homogenous PTSA acid-KOH

of the esterified layer to recover FAME, and (iv)
transesterification of residual oil using potassium hydroxide
(KOH). This process involved additional step of
transesterification with KOH, to convert the residual oil
to FAME, which increased the yield to 90-95 per cent.
Thus, PROCESS-III gave 10 to 15% higher yield than
PROCESS-I and PROCESS-II, wherein the last step of
transesterification of residual oil was omitted. PROCESS-
III was also used in converting waste cooking oil.
Description of Plant
Figure 2 shows the process flow diagram of the plant that
could perform any of the above processes. The resources
required to install and operate the plant were (a) land area
of about 186 sq.m, (b) raised production shed with roof for
rain protection, (c) water requirement of about 400 l / batch
of 400 l of biodiesel, (d) installed power of 8 kVA (to run
thermic fluid pump, (e) ID fan for handling wood combustor
smoke, (f) vaccum pump, cooling water circulation pump,
reactor pump and lights, and (g) firewood at the rate of
about 30 kg/batch. The fixed capital engaged, without
considering land cost, was Rs 15 lakh.
The esterification and transesterification reactions were
carried out in two identical reactors (R1 and R2 in Fig. 2).
The raw material was heated to 70°C using hot thermic
fluid, which in turn was heated employing a firewood
combustor. The distillation columns (C1 and C2) were
employed for the recovery of FAME and methanol,
respectively. The methanol recovery from the neutralized

38
N.G. Shah, Shoyeb Khan and S.M.Mahajani JAE : 47 (2)

Fig. 2: Flow sheet of pilot plant (400 l/batch) commissioned at users site

39
April-June, 2010 Biodiesel Making from Waste Vegetable Oils: A Case Study of Lab to Plant Technology Transfer
methanol layer in esterification step was performed in
column C1 over a temperature range of 64 oC -100 oC.
The reboiler temperatures maintained during distillation
was close to 270°C. The plant piping, reactors and reboilers
were insulated to reduce heat losses to the surroundings.
The total wood requirement was thus restricted to only
25-30 kg (dry wood having moisture content of less than
20%) per batch of 400 litre. Biodiesel from five different
raw materials (acid oil, waste cooking oil, jatropha, karanja
and palmoline oil) was made in the pilot plant installed at
YMC, Yava, Moharashtra. The later three are the potential
raw materials being considered by Indian manufacturers.
They were also studied to compare the results with the
first two cheaper feedstocks, i.e. waste-oils.
RESULTS AND DISCUSSION
Material Balances
The material balances for biodiesel making in all the three
processes are given in Fig.3a, 3b and 3c, respectively. As
indicated in Fig.3a (PROCESS-I), for 100 parts of acid oil
170 parts methanol was added for esterification, out of
which 155 parts of methanol was recycled from the previous
batch and 10 parts was added afresh. H2SO4 (0.5 part) was
added for the first process. As indicated in Fig.3b, for
PROCESS II, 100 parts of acid oil was used for the
esterification reaction where 170 parts methanol was added,
out of which 160 parts of methanol came from recycle of
the previous batch and 10 parts was added afresh. PTSA (1
part) was added in the PROCESS-II. Methanol (160 parts)
was recovered by distillation and reused in the next batch.
FAME recovered by vacuum distillation was 75 parts and
the residual oil produced was 20-25 parts. Methanol (5
Fig.3(a): Material balance for PROCESS-I
40
parts) was recovered by distillation from glycerol layer and
was reused in transesterification. The total FAME recovered
after transesterification was 95 parts. Figure 3c depicts the
mass balances in biodiesel making from waste cooking oil,
made by PROCESS III. Compared to other raw materials,
it was found that 9 parts of glycerol layer was formed as a
by-product in this conversion. The ester layer was distilled
under vacuum to give 90 parts of biodiesel.
Plant Performance
The biodiesel from acid oil and waste-cooking oils was
produced in a batch mode. The capacity of the plant was to
produce 400 l/day, and the batch time was close to 12-16
hours. On an average, the process time for both
esterification and transesterification was about 2.5-3 hours.
The distillation process was for about 3 h when the reboiler
temperatures were in the range of 270°C and at a vacuum
of 720-750 mm Hg. Recovery of methanol by distillation
took about 2.5 hours. Thus, the total time required to
complete all the steps in a given batch was about 12-16
hours. One trained technician and 1 helper per batch could
accomplish all the steps. With proper scheduling, the
capacity can be increased to two batches per day. The
characteristics of biodiesel made from various raw materials
are given in Table 1. Calorific value of bio-diesel ranged
between 35-42 MJ/Kg. As indicated in Table 1, while
density and flash point were within the range prescribed
by BIS, the kinematic viscosity and moisture content
exceeded slightly.
Since the bio-diesel plant has a distilation column as an
integral component of the process, the `end-product’ is fairly
uniform no matter what raw material was used. This is
N.G. Shah, Shoyeb Khan and S.M.Mahajani JAE : 47 (2)

Fig.3(b): Material balance for PROCESS-II and PROCESS-III

Fig.3(c): Material balance for making biodiesel from waste cooking oil

Table 1. Characteristics of biodiesel made from different raw materials

Sample Density Calorofic Kinematic Flash point Moisture

(g/cc) Value viscosity (oC) content
(mj/kg) (cSt) (%)

BIS standard 0.87 – 0.90 - 3.5-5.0 > 100 0.05

Palm biodiesel 0.86 40.1 7.02 124 0.35

Acid oil biodiesel 0.85 39.1 5.35 115 0.32

WCO* biodiesel 0.86 39.6 5.09 118 0.36

Jatropha biodiesel 0.86 39.5 7.21 130 0.17

Karanja biodiesel 0.86 39.4 6.44 126 0.41

* Waste Cooking oil

41
 April-June, 2010 Biodiesel Making from Waste Vegetable Oils: A Case Study of Lab to Plant Technology Transfer
evident from relatively similar calorific values of all bio-
diesels (Table 1) when the raw materials varied. This
demonstrated the plant’s potential to make bio-diesels of
fairly uniform characteristics and meet the BIS standards.
A diesel engine (7.46 kW, 1365 cc, run on B100 mode)
coupled with a genset (Mahindra Powerall) burnt all
biodiesel samples without any difficulties. The engine
genset has so far logged 95 h on B100 biodiesel mode.
With this installation, around 120,000 l/year of biodiesel
can be produced. Raw material requirements can be met
by tying-up with supplier of acid oil (vegetable oil makers)
and waste cooking oils from city-based chain restaurant
units.
Assessment of Processes Alternatives
If the feedstock contains large amount of FFA, one can use
either process I or process II mentioned above. Process I
used a very strong acid catalyst (sulphuric acid), and hence
the reaction time was relatively less. However, sulphuric
acid being corrosive, one needs to neutralize it with calcium
hydroxide to avoid corrosion of the equipment (e.g.
distillation unit) used in downstream processing. This adds
to the processing and equipment cost. On the other hand,
PTSA based process (Process II) did not need additional
neutralization step. A simple washing step could remove
PTSA, if necessary. In both Process-I and II, the option of
using unreacted oil as a soapstock existed. If necessary, it
can be stored and converted to biodiesel after few batches
by a transesterification step. If the FFA is relatively less
than 10-15% (e.g. waste cooking oil), then the two step
process (process-III) utilizing both FFA and oil from the
feedstock is recommended.
CONCLUSIONS
The study explored using unconventional raw materials
such as acid oils and waste cooking oils for the production
of biodiesel. Most of the non-edible oils produced in India
have high free fatty acid content, and the conventional
process using base (KOH/NaOH) catalyst form salts that
hinders in settling process. The proposed two-step method
of conversion, with a yield of about 70 %, was demonstrated
at a pilot scale (400 l/batch). Technical feasibility of the
plant using both conventional as well as unconventional
raw materials was established. The unit is being evaluated
by a village entrepreneur to assess the economic
sustainability of the biodiesel unit installed in a village
industry centre. If the raw material availability is ensured
on a sustained basis, the product will easily find market in
the vicinity of the production facility.
42
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ACKNOWLEDGEMENT
The authors acknowledge the funding received from Khadi-
Village Industries Commission (KVIC-Mumbai) for the
plant construction and testing. The support received from
Yusuf Meherally Centre (YMC-TARA village, Raigad
district, Maharashtra) for providing the site for plant
installation and their staffs during testing is duly
acknowledged. Authors also acknowledge the help from
Ch. Srinivas (M. Tech student at IIT-Bombay, 2008-09), in
measurement of biodiesel properties.
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