Biofuels

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Lab-scale catalytic production of biodiesel from

waste cooking oil – a review

Abdul Raqeeb Mohammed & Chakradhar Bandari

To cite this article: Abdul Raqeeb Mohammed & Chakradhar Bandari (2017): Lab-
scale catalytic production of biodiesel from waste cooking oil – a review, Biofuels, DOI:
10.1080/17597269.2017.1370882

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Published online: 14 Sep 2017.

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 BIOFUELS, 2017
https://doi.org/10.1080/17597269.2017.1370882

Lab-scale catalytic production of biodiesel from waste cooking oil – a review

Abdul Raqeeb Mohammed and Chakradhar Bandari
Ramky Enviro Engineers Ltd, Gachibowli, Hyderabad, Telangana, India, 500032

ABSTRACT ARTICLE HISTORY

The adverse effects of fossil fuels on the environment and the rapid exhaustion of oil reserves Received 4 February 2017
are major concerns in the current global energy demand scenario. As a result, biofuels have Accepted 4 August 2017
emerged as promising alternate fuel due to their renewability, clean emissions and economic KEYWORDS
advantages over petroleum diesel. Biofuels are obtained from renewable sources such as Biodiesel; transesterification;
vegetable oils, animal fat, microalgae, etc. Amongst these, waste cooking oil is considered to be catalyst; fatty acid methyl
an economical feedstock. This review focuses on different pretreatment methods for waste ester; free fatty acid; waste
cooking oil and its lab-scale catalytic transesterification to biodiesel. Homogeneous, cooking oil
Downloaded by [Australian Catholic University] at 13:49 18 September 2017

heterogeneous and enzymatic catalysts are compared based on reaction conditions, method
employed and product yield. The purification steps, biodiesel properties and engine emissions
profile are also discussed.

Introduction could lead to performance issues [31,32]. Usually, bio-

Fossil fuels account for almost 80% of worldwide
energy consumption [1,2]. It is estimated that between
2010 and 2030, the global energy demand will increase
by 40%, leading to scarcity of non-renewable fossil fuel
reserves in the next few decades [3]. Fossil fuel emis-
sions have also been reported to be responsible for
environmental pollution and global warming. This has
resulted in a search for alternative sources of energy,
preferably in a renewable form [4–12]. The transporta-
tion sector is reported to currently account for more
than 61% of worldwide fossil fuel consumption [1,2].
Hence, the search for alternative fuels, especially those
that may be used in the transportation sector, has
become a worldwide quest [13]. Amongst the various
alternatives investigated, biodiesel has emerged as a
sustainable alternative to fossil fuels.
Biodiesel has significant advantages over conven-
tional petroleum fuels, such as substantial reduction in
greenhouse gas emissions, non-sulfur emissions, non-
particulate matter pollutants, low toxicity, biodegrad-
ability and renewability [14–23]. This advantage is also
reflected in fuel properties such as exhaust emissions,
octane number, flash point, lubricity characteristics,
etc. [24–26]. Biodiesel is the first alternative fuel to pass
the health effects testing requirements of the Clean Air
Act Amendments of 1990 [27]. The physicochemical
properties, efficiency and energy content of biodiesel
are similar to those of petroleum diesel fuel [28–30].
Hence, biodiesel is a good alternative to petroleum die-
sel and can be used to run compression ignition
engines without any modifications. However, neat bio-
diesel is not directly used in diesel engines as this
diesel is blended with petroleum diesel in some pro-
portion for use in automobile engines [33,34]. Such
blends are commercially available in countries such as
USA, Germany, Brazil and France, and reduce fossil fuel
consumption. For example, India currently imports
nearly 70% of its annual petroleum crude oil require-
ments, and this costs nearly US $12 billion per year.
Blending of 5% biodiesel with petroleum diesel could
help save US $0.6 billion per year for India [35].
Fatty acid alkyl esters derived from esterification/
transesterification of fatty acids/triglycerides with alco-
hol and a suitable catalyst result in the formation of
biodiesel [36–38]. This review focuses on catalysts that
could be used on a lab scale to produce biodiesel from
waste cooking oil (WCO). The possible feedstocks, pro-
duction and purification processes and exhaust emis-
sions of engines fueled with biodiesel are also
discussed here.
Feedstocks
Biodiesel can be produced from various triglyceride
sources such as vegetable oils (edible, non-edible or
waste oils), animal fats (mostly edible fats or waste
fats) and microalgae [39–41]. There are more than 350
oil-bearing crops identified, among which oil derived
from sunflower is widely used for cooking purposes
[42]. Some of the edible oil sources reported as feed-
stocks for biodiesel are corn, sunflower, coconut,
tobacco seed, peanut, palm, soybean, canola and rape-
seed [43,44]. Non-edible oils such as crude jatropha oil,
crude palm oil, karanja (Pongamia) oil and waste

CONTACT Abdul Raqeeb Mohammed raqeeb.mohammedabdul@ramky.com

© 2017 Informa UK Limited, trading as Taylor & Francis Group
 2 A. R. MOHAMMED AND C. BANDARI

Table 1. Conventional and non-conventional feedstocks. Table 2. Main properties of waste cooking oil (WCO).
Conventional feedstock Non-conventional feedstock Property Units of measurement Value
Mahua Lard Density g/cm3 0.91–0.924
Piqui Tallow Kinematic viscosity (40
C) mm2/s 36.4–42
Palm Poultry fat Saponification value mg KOH/g 188.2–207
Karang Fish oil Acid value mg KOH/g 1.32–3.6
Tobacco seed Bacteria Iodine number g I2/100 g 83–141.5
Rubber plant Algae
Rice bran Fungi
Sesame Microalgae
Safflower Tarpenes
Barley Latexes also help meet the energy challenge [42,44]. Further-
Coconut
Laurel more, the use of WCO for biodiesel production reduces
Used cooking oil the inter-competition between the oil resources and
Soybean
Rapeseed
edible oil-based food crops [61].
Canola Vegetable oils from different sources exhibit differ-
Babassu ent properties [43]. WCO contains various types of tri-
Brassica carinata
Brassica napus glycerides, a small amount of glycerol, FFA, and fatty
Copra acid esters which vary in carbon chain length and
Groundnut
Cynara cardunculus unsaturation [62,63]. The frying process leads to chemi-
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Cottonseed cal reactions such as polymerization, hydrolysis, oxida-

Jatropha nana
Jojoba oil
Pongamia glabra
animal fat have also been identified as effective feed-
stocks for biodiesel production [45,46].
The ability of this feedstock-based biodiesel to
replace petroleum diesel would be decided by the eco-
nomics of the production process. It has been reported
that nearly 70 to 95% of the total cost of this product
would be taken up the cost of the raw material [47].
Hence, a liter of edible oil, which needs to be proc-
essed further to obtain biodiesel, costs more than a
liter of petroleum diesel [45]. An effective alternative to
feedstock would be the utilization of WCO as raw
material. WCO, which costs a fraction of the cost of edi-
ble oils, is likely to be an economical feedstock for bio-
diesel production [48,49]. The WCO-based biodiesel
would convert waste to a usable and green fuel. The
utilization of catalysts derived from waste materials
has also been explored to make the process more eco-
nomical and sustainable [8,36]. Table 1 shows a list of
conventional and non-conventional feedstocks [50].
tion, etc., and leads to modifications of the physical
and chemical properties of the oil [4,6].
Due to chemical reactions such as polymerization,
hydrolysis and oxidation occurring in the oil during the
frying, the properties of fresh oil and WCO are different
[3,4]. The important physical and chemical properties
of WCO provided in Table 2 depict the typical values
for WCO properties: density, kinematic viscosity, sapon-
ification value, acid value and iodine value [5].
During frying of oil, the amount of heat and the
moisture content of the oil increase the oxidation and
hydrolysis of triglycerides, leading to an increase in the
FFA content [52]. High FFA in the feedstock is consid-
ered to be the biggest challenge in using WCO for bio-
diesel production [64]. WCO contains acids such as
myristic (tetradecanoic), palmitic (hexadecanoic), stea-
ric (n-octadecanoic), oleic, linolenic, arachidic and
other fatty acids, among which oleic and linolenic are
identified as the major components [5]. It has also
been reported that the composition of unsaturated
FFA in WCO may be as high as 93.1%, leading to high
iodine values [51].

Biodiesel production process

Waste cooking oil
WCO refers to the oil residue obtained after being used
for cooking food. After repeated use, cooking oil accu-
mulates free fatty acids (FFA), making it unsuitable for
further use [35]. The sources of WCO are restaurants
and food-processing industries [51]. The WCO is unfit
for human consumption and is usually disposed of in
landfills and waterways. However, this leads to soil and
water pollution and disrupts the aquatic ecosystem
[52–55]. As a result, WCO disposal into waste drainages
is penalized in some developed countries. Instead, the
WCO may be redirected as feedstock for biodiesel [56–
60]. This strategy would obviate the necessity for dis-
posal of environmentally unfriendly WCO, and would
Biodiesel can be produced in batch mode as well as
continuous mode. Most of the lab-scale production
processes are conducted in batch mode as it is rela-
tively simple and inexpensive to operate. However, the
feedstock requires pretreatment before it can be proc-
essed [4].
Pretreatment of WCO
The quality of the feedstock determines the optimum
values of the operating parameters that affect the
product yield [2]. In pretreatment, the oil is filtered to
remove any chunks of food particles and other insolu-
ble impurities by passing it through a cotton cloth

[41,58]. The oil is usually preheated to a temperature
above 100
C to reduce the moisture content to
500 ppm [33,38]. Dissolved solids such as salts in oils
may be removed by the addition of water followed by
silica gel. The mixture is stirred continuously for 3 h
and subjected to vacuum filtration to isolate the silica
gel and water [29]. The de-coloration of oil is achieved
by stirring the oil with 5% activated clay at 80–110
C
for 25 min [52]. The acid value of FFA determines the
type of catalyst selected for transesterification reac-
tions. Hence, it is an important parameter. The FFA
(acid value) content is determined by titration with
standard American Oil Chemist Society Cd 3d-63 and
American Society for Testing Material D664 methods
[9,15]. The titration is performed with 10% oil in isopro-
pyl alcohol with few drops of phenolphthalein indica-
tor against standard KOH or NaOH solution. The titer
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value is used to calculate the acid value (mg of KOH or
NaOH/g of oil) of the oil, as shown in Equation (1) [33]:
NaOH ðMW Þ  NaOH ðMÞ  Titration volume ðml Þ
(1)
oil sample ðgÞ
Esterification and transesterification of WCO
The FFA in biodiesel may be deposited into and dam-
age the vehicle engine. Hence, an upper limit on the
FFA content in biodiesel is specified. In WCO, the FFA
contents are converted to alkyl esters (biodiesel) in the
presence of alcohol and a catalyst, as shown in Figure 1
[56]. The transesterification reaction of oil with alcohol
in the presence of a catalyst to produce alkyl esters
(biodiesel) and glycerol is shown in Figure 2 [65].
The reaction involves two immiscible phases, an
alcohol phase and an oil phase. A catalyst is necessary
to enhance the miscibility and accelerate the reaction
[66]. Usually, this reaction takes place with the use of a
chemical catalyst at a relatively high temperature, near
the boiling point of alcohol [55]. Methanol is widely
used because of its relatively low cost and some advan-
tageous physical and chemical properties over other
alcohols [67]. The transesterification process depends
on many parameters including temperature, pressure,
duration of reaction, agitation, molar ratio of alcohol to
oil, type of alcohol, catalyst concentration, moisture
content and FFA content in the feed oil.
Some of the acid catalysts used for transesterifica-
tion are sulfuric acid, hydrochloric acid and sulfonic
Figure 1. Schematic representation of the esterification reaction [56].
BIOFUELS 3
acids. Ionic liquids such as 1-Butyl-3-methylimidazo-
lium hydrogen sulfate ([BMIM]HSO4) have also been
reported to catalyze transesterification reactions [2,16].
For FFA content of less than 1%, the feedstock can be
directly transesterified with an alkali catalyst [6]. The
reaction is reversible and this may be minimized by
optimizing the oil-to-methanol ratio, the amount of
catalyst and the reaction temperature [34,56]. The FFA
conversion is calculated using Equation (2), where ‘ao’
is the acid value of the oil layer and ‘aw’ is the acid
value of the WCO [68]:
 
ao
% FFA Conversion ¼ 1  100 (2)
aw
The alkali-catalyzed transesterification is carried
with a solution of KOH in alcohol added into a stirred
reactor containing heated WCO. In the case of other
types of catalysts, the alcohol is added to the WCO at
the start of the reaction [4,5,13]. In the case of metha-
nol, the reaction is carried out at between 55 and 65
C.
The transesterification reaction is reported to have
been carried out in laboratory- and pilot-scale reactors.
Laboratory-scale transesterification has been reported
in batch reactors, bubble column reactors, etc. The
pilot-scale transesterification reaction has been
reported with reactive distillation and ultrasound reac-
tors. A three-necked, round-bottom flask with a water
bath and a magnetic stirrer is a widely employed lab-
scale batch reactor. The nature of the catalyst plays a
significant part in determining the yield and the eco-
nomic feasibility of these reactions [8].
One-step catalysts
Three types of catalysts are utilized in biodiesel pro-
duction: homogeneous, heterogeneous and enzymatic
catalysts [61].
Homogeneous catalyst
Homogeneous catalysts, as the name suggests, have
the catalyst in the same medium as the reaction mix-
ture and are of two types, alkaline and acidic. Alkaline
catalysts include bases such as sodium hydroxide,
potassium hydroxide, sodium methoxide and potas-
sium methoxide, and acidic catalysts include sulfuric
acid and hydrochloric acid [4,10]. The major advan-
tages of the homogeneous catalysis are moderate
 4 A. R. MOHAMMED AND C. BANDARI

Figure 2. Schematic representation of the transesterification reaction [65].

reaction temperatures of 40 to 60
C, moderate atmo- Table 3. Comparison of various reaction conditions for biodie-
spheric pressure conditions, relatively reduced dura- sel production using homogeneous catalysts.
tion of reaction, availability of inexpensive catalyst and Catalyst
Type of reactor used M:O C T t Y Ref.
high yield [25,29,45,69]. Hence, this process is used
Lab-scale batch NaOH 6:01 1 60 1–3 80 [4]
worldwide for biodiesel production, especially for Lab-scale batch NaOH 15:01 0.69 55 1–1.5 94 [5]
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large-scale production [26,62]. However, homoge-
neous alkaline catalysts are only effective for refined
vegetable oils with less than 0.5–0.6 wt. % FFA content
and 0.06 wt. % water content [22,70]. With high FFA
content, a saponification side reaction occurs, leading
to excess catalyst consumption and reduced yields
[71]. A low amount of catalyst may lead to low yield;
however, a higher amount of catalyst may result in
saponification. Hence, the final product yield depends
strongly on the amount of catalyst and FFA content
present in the feed [5]. Some reports have shown that
a maximum of 3 wt. % FFA can be tolerated by the
alkaline catalyst [72–77]. A major drawback of homoge-
neous alkaline catalyst is its inability to be recovered
for reuse [42,48]. The basic catalyst is dissolved in the
biodiesel as well as glycerol fractions at the end of the
reaction. The basic catalyst may be removed with
repeated washing with water. However, this additional
step would also lead to loss of the biodiesel product in
the wash water, an increase in energy consumption,
and the generation of environmentally toxic effluent
waste water [29,45]. The basic catalyst would also lead
to corrosion of the reactor [69]. The removal of alkali
metals from finished biodiesel is crucial because high
catalyst content in the product can result in the forma-
tion of carbon residues in the fuel injection lines of
automobiles. Interestingly, these problems have been
reported to be absent when ionic liquids are used as
catalysts in biodiesel production [78].
A comparison of the performance of various homo-
geneous base catalysts and the corresponding reaction
conditions for biodiesel production using WCO as feed-
stock is provided in Table 3. It is apparent that at a
higher molar ration of methanol to oil (12:1–15:1) with
sodium hydroxide as the catalyst, a biodiesel yield up
to 95% can be obtained in a short duration of reaction
(1.5–2 h) [5,33]. Potassium hydroxide is equally effec-
tive for biodiesel production from WCO [6]. For transes-
terification using a homogeneous catalyst, a
temperature of 55–65
C has to be maintained [4–
Round-bottom KOH 6.18:1 1 66.5 1 92.76 [6]
flask
Lab-scale batch KOH 3:01 0.4 60 8 91.08 [13]
Round-bottom KOH 7:01 0.75 80– 0.5– 91– [54]
flask 90 0.83 92
Dissolution NaOH 12:01 1 60 2 95 [33]
apparatus
M:O: methanol to oil molar ratio; C: catalyst concentration (%w/w of
oil); T: temperature (
C);
t: time (h); Y: yield (wt. %).
6,13,33]. A dissolution apparatus retrofitted as a multi-
ple bioreactor produced 95% biodiesel in 2 h with 1%
NaOH. For studies on the rate of the reaction, eight
reactors of 1-L capacity each were used [3].
Among the homogeneous acid catalysts, sulfuric
acid, hydrochloric acid and super phosphoric acid are
widely used [41]. They are known for simultaneous
catalysis of esterification and transesterification reac-
tions [27]. The most commonly used acid is sulfuric
acid [47]. The benefits of using acid catalyst are high
conversion and low costs [68]. In the esterification of
oil using acid catalyst, water is a byproduct [21]. How-
ever, the presence of water does not hinder the perfor-
mance of the acid to catalyze the transesterification
reaction. However, in comparison with alkaline cata-
lysts, acid catalysts require a longer duration for reac-
tion and are less efficient [25,42,46,69,74]. Other
disadvantages of using acid catalysts are effluent dis-
posal problems, high reaction temperature, expensive
material required to construct equipment capable of
handling acids, and difficulty in catalyst recovery for
reuse [64,71].
Heterogeneous catalysts
Heterogeneous catalysts are usually solid catalysts
which are insoluble in the liquid reaction mixtures and
are of two types, acid and base catalysts. Some hetero-
geneous catalysts are metal oxides such as Al2O3, ZnO-
La2O3, CaO, zeolites, superacids such as sulfated zirco-
nia, niobium acids, tripotassium phosphate, Mg-Al
hydrotalcite, K+-impregnated zirconia, ion exchange
resins, etc. [8,12,64,65,70,79–81]. Usually, porous
 BIOFUELS 5

materials are preferred in solid catalyst manufacturing
due to their high surface area per volume. An ideal
solid catalyst should have numerous active sites, high
stability and high hydrophobicity, and should be meso-
porous and relatively inexpensive [80]. The advantages
of heterogeneous solid catalysts are facilitation of bet-
ter separation of product [27,45], recovery and reus-
ability of catalysts [75,82], no corrosion of the reactor
[27], better quality of the final products [79,80], simul-
taneous conversion (esterification and transesterifica-
tion) of high-acidic oil [75,76], no soap formation [83],
ecofriendly nature [75,84], and less energy and water
consumption [45]. In addition to this, they have a high
tolerance to FFA and water [43,76] and are easy to
regenerate [84].
In comparison to homogeneous catalyst processes,
heterogeneous catalysts have a requirement of
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as 10 h. The byproducts glycerol and lauric acid were
converted to triglycerides using the SMTSA catalyst to
address the problem of glycerol disposal. Glycerol con-
verted to triglyceride can be used further as feedstock
for biodiesel production. SMTSA catalyst can be reused
up to 3 times [41]. Calcium oxide as a catalyst for bio-
diesel production has shown many advantages over
other heterogeneous catalysts, such as long catalyst
life, high catalytic activity and moderate reaction con-
ditions, and it is also relatively inexpensive [44,72].
Zinc stearate immobilized on silica gel (ZS/Si) has
also been reported to show good catalytic perfor-
mance and produce biodiesel with 98 wt. % yield, and
the catalyst was reusable up to 4 times [27]. It has been
reported that zinc aluminate (ZnAl2O4) as catalyst pro-
duced a yield as high as 95% with a reaction duration
of 2 h, and that the catalyst could be used for up to

extreme reaction conditions [3,43]. The catalyst prepa-
ration is expensive and complex [85] and needs sophis-
ticated equipment for characterization [29,43,86,87]. It
requires a very high calcination temperature for cata-
lyst synthesis [45], and a high reaction time [44,45,83].
The processes that have been employed on a lab
scale for the simultaneous esterification and transester-
ification of WCO using heterogeneous catalysts are
mentioned in Table 4. It can be inferred that heteroge-
neous catalysts need a higher methanol-to-oil molar
ratio, higher temperature, higher catalyst amount and
longer duration of reaction. However, a higher yield of
biodiesel can be obtained with high-acidic-content
feedstocks. Silica melamine trisulfonic acid (SMTSA)
catalyst has been reported to produce the highest
yield of 98 wt. % with a duration of incubation as high
three cycles. The methanol-to-oil molar ratio utilized
was 40:1. The results from this process also show that
there was no significant difference in yield between
methanol-derived biodiesel and ethanol-derived bio-
diesel [30].
Biocatalyst derived from eggshells has been used as
catalyst for transesterification to obtain biodiesel, with
97.5 wt. % yield [42]. This catalyst provided the solution
to three major problems in catalyst production: envi-
ronmental, economic and waste management. The
process conditions were optimized using LINGO soft-
ware, which predicted a yield of 98.8% at a methanol-
to-oil molar ratio of 6:1, 3 wt. % catalyst concentration,
and a mixing rate of 350 rpm at 60
C for 30 min. How-
ever, the actual yield obtained from the experimental
work was 97.5 wt. %.

Table 4. Comparisons of various reaction conditions for transesterification of waste cooking oil (WCO) using heterogeneous
catalysts.
Type of reactor Catalyst used M:O C T t Y Ref.
Lab-scale batch Heterogeneous catalyst: b- Ca3(PO4)2 from chicken bones 15:1 5.0 65 4 89.3 [8]
Continuous-reaction apparatus Sulfonated rice husk (RHC–SO3H) derived from rice husk char 20:1 5 110 15 90 [12]
Round-bottom flask Cs0.6Zr0.4/Al2O3 30:1 3 65 3 90 [43]
Round-bottom flask Bifunctional catalyst (Mo-Mn/gamma –Al2O3-MgO) 27:1 15 100 4 91.4 [29]
Round-bottom flask CaO derived from eggshells 12:1 5 65 1 94.5 [45]
Batch reactor Zinc stearate immobilized on silica gel (ZS/Si) 18:1 3 200 10 98 [27]
Batch reactor K2O/CaO-ZnO 15:1 2 60 4 81.0 [72]
Round-bottom flask KBr-impregnated CaO 12:1 3 65 1.8 82.4 [65]
Lab-scale batch Sr/ZrO2 29:1 2.7 115 2.8 79.7 [63]
Stainless steel batch reactor ZnAl2O4 40:1 10 150 2 95 [30]
Round-bottom flask K3PO4 6:1 4 60 2 97.3 [83]
Round-bottom flask Amberlyst 15 12:1 3 65 9 78 [71]
Closed reactor Calcined scallop shell (CSS) 6:1 5 65 2 86 [82]
Round-bottom CsPW/B (inclusion complex of 9:1 3 65 3 96.9 [68]
flask Cs2.5H0.5PW12O40 with bridged bis- cyclodextrin)
Lab-scale batch CaO, glycerol and methanol at a mass ratio of 1:1.6:13.4 7:1 0.4 60 2 89.0 [39]
Laboratory stirred autoclave Silica melamine tri sulfonic acid (SMTSA) 10:1 5 130 10 98 [41]
Round-bottom flask Biocatalyst from egg-shells 6:1 3 60 0.5 97.5 [42]
Round-bottom flask CaO derived from white bivalve clam shell 12:1 7 65 1 94.25 [44]
Glass batch reactor Ba/CaO construction waste) 9:1 3 65 3 88 [58]
Stainless steel batch reactor TiO2–MgO 50:1 10 160 6 92.3 [59]
Stainless steel batch reactor SO42¡/SnO2–SiO2 9:6:1a 5 150 1 81.4 [74]
Stainless steel batch reactor SO42/SnO2 – SiO2 [3] 15:1 3 150 3 92.3 [76]
Round-bottom flask (Li, Na and K) supported by rice husk 9:1 3 65 3 96.5–98.2% [84]
Batch autoclave Calcined raw clay 15:1 3.5 150 5 96 [85]
Stainless steel batch reactor Mn1.4Zr0.35Al0.6O3 14:1 2.5 150 5 93 [94]
M:O: methanol-to-oil molar ratio; C: catalyst concentration (%w/w of oil); T: temperature (
C);
t: time (h); Y: yield (wt. %); a: ethanol to methanol to oil.
 6 A. R. MOHAMMED AND C. BANDARI
Enzymatic catalysts
Enzymes are biological catalysts capable of catalyzing
biochemical reactions. Over the last few years,
enzymes have been employed for the large-scale pro-
duction of various organic compounds, including bio-
diesel [88]. Enzyme-catalyzed biodiesel production
does not lead to saponification, and simplifies the bio-
diesel purification process [1,69,89]. Hence, the enzy-
matic process does not need a water-washing step and
can esterify triglycerides and FFA. Some of the advan-
tages of using enzymes are tolerance to high FFA, mild
reaction conditions, eco-friendliness and reusability
[1,89,90].
Laboratory-scale enzyme-catalyzed (Novozyme435)
biodiesel production has been reported in the litera-
ture [1,60,90,91]. Table 5 shows the reaction conditions
for biodiesel production using WCO in a lab-scale pro-
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cess. It can be inferred from the table that a continuous
enzyme-catalyzed process can produce a high yield of
biodiesel in a short duration of time. Enzyme catalysts
need a lower methanol-to-oil molar ratio and lower
temperatures, but a large amount of catalyst and a lon-
ger duration of reaction are required to achieve the
desired conversion. It has been reported that a high
yield of up to 90% can be produced in 4 h in a semi-
continuous reactor, and the catalyst can be reused up
to 7 times [91].
A batch process utilizing a glass reactor equipped
with a six-bladed turbine impeller has been reported
for transesterification reaction. The methanol deactiva-
tion can be omitted by using dimethyl carbonate
(DMC) in place of methanol, and a yield of 77.87 wt. %
was achieved. The catalyst could be reused up to
6 times in this process. Some disadvantages of the
enzyme-catalyzed process are the high amount of
enzyme required, high cost of the enzyme, its denatur-
ation by the alcohol, and the relatively low yield when
compared with homogenous and heterogeneous solid
catalysts [1,42].
Catalysts used for two-stage process
For feedstocks containing high FFA content, a two-step
process is employed in which the FFA is initially esteri-
fied with an acid catalyst, followed by transesterifica-
tion using a base catalyst. This process has been
Table 5. Comparison of reaction conditions for biodiesel production from waste cooking oil (WCO) using enzymatic catalysts.
Process Batch
Reactor Microporous resin beads
Amount of oil 2g
Catalyst Novozyme435
Alcohol-to-oil molar ratio 6:1 (DMC to oil)
Temperature (oC) 60
Time (h) 24
Yield (wt. %) 77.87
Ref. [1]
reported in numerous papers and is widely applied in
industry. The catalyst used for esterification and trans-
esterification reactions can be either homogeneous or
heterogeneous. A comparison of the lab-scale process
conditions of this two-step process with various cata-
lysts is provided in Table 6. The table also lists the
parameters for esterification, followed by those for
transesterification. The table also shows that the two-
step process may be time consuming, but it is effective
for high FFA feedstocks. It has been reported that a
high yield of biodiesel, i.e. 95 wt. %, can be achieved
using sulfuric acid for esterification and calcinated sea
sand (CaO) for transesterification. The esterification
step resulted in an acid value as low as 0.08 mg KOH/g
of oil [3].
An eco-friendly and efficient process using the het-
erogeneous acid catalyst 25 wt. % TPA/Nb2O5 for ester-
ification and the heterogeneous base catalyst 20 wt. %
ZnO/Na-Y zeolite for transesterification has been
reported. This process provides 94 wt. % biodiesel
yield, and the catalyst can be reused up to 6 times [75].
A continuous process using a microtube reactor for
esterification and transesterification has also been
reported [47], with a product yield of 91.76 wt. %. The
process utilized sulfuric acid for esterification and
potassium hydroxide for transesterification steps using
moderate reaction conditions and a relatively shorter
duration of incubation.
Purification of biodiesel
A high-purity biodiesel product is necessary to ensure
fuel quality and engine life. The impurities encoun-
tered in crude biodiesel are methanol, glycerol, metal
ions, soap, FFA, catalysts, water and unconverted glyc-
erides [67].
Upon completion of the reaction, the products sepa-
rate into two immiscible layers, a relatively less dense bio-
diesel layer on top, and a more dense glycerol layer at the
bottom [4–6]. Separation is usually achieved by allowing
the layers to settle under gravity in a separatory funnel for
around 20 to 24 h at room temperature [4–10,92–94].
Solid catalysts may be recovered by centrifugation, say at
6000 rpm for 20 min as reported in literature [83]. Vacuum
filtration followed by drying in an oven at 50
C also pro-
vides enhanced recovery of the solid catalysts [30]. These
Batch Continuous Continuous
Screw-capped vial system Packed bed reactor Semi-continuous
1.5 mL 0.57 mL min-1 110 mL
Novozyme435 Novozyme435 Novozyme435
12:1 (methanol to oil) (4:1) methanol to oil; (1:1) tert-butanol (8:1) methanol to oil
40 40 44.5
24 4 4
47 79.1 90
[90] [60] [91]
 BIOFUELS 7

Table 6. Comparison of reaction conditions for two-step esterification and transesterification of waste cooking oil (WCO).
Reactor type Round-bottom flask Spherical reactor Three necked, round bottom Microtube reactor Parr reactor
Process Batch Batch Batch Continuous Batch
e H2SO4 H2SO4 SrFe2O4/SiO2SO3H H2SO4 TPA/Nb2O5
Catalyst used t NaOH Calcinated sea sand NaOH KOH ZnO/Na-Y
e 6:1a 15:1 10 mL: 5 mL* 9:1a 14:1
Methanol-to-oil molar ratio t 12:1 8 mL: 5 mL* 24:1
e 50a 60 100 65 65
Temperature (
C) t 60 60 65 65
Time (h) e 1.5a 3 1.5 5 sec 5
t 6 0.66 5 sec 12
Yield (wt. %) 89.8 95.4 »100% (conversion 91.76 94
Ref. [11] [3] [79] [47] [75]
Note: 'e': esterificaion; 't': transesterification; 'a': simultaneous reaction; '*': oil to methanol volume ratio.

layers are washed with water at high temperature with Table 7. American Socitey for Testing Materials standards for
stirring followed by phase separation [28,67]. The techni- biodiesel.
ques used on an industrial scale for refining crude biodie- Property Standard value Unit of measurement
sel are wet washing, dry washing and membrane Density 0.87 g/cc
Viscosity 1.9–6.5 mm2/s
extraction. Among these techniques, water washing is the Cetane index > 47 No unit
most widely used method. In the wet washing technique, Carbon residue (100% sample) 0.050 wt. %
Downloaded by [Australian Catholic University] at 13:49 18 September 2017

Acid value 0.50 (max) mg KOH/g

the crude biodiesel is neutralized with phosphoric or sul-
furic acid to remove to the soap. In dry washing, silicates
and ion exchange resins are used for purification. Applica-
tion of both dry washing and wet washing can effectively
purify the product, but leads to an increase in the overall
production costs [69]. The washing step is essential for
WCO-derived biodiesel to meet product specifications
such as visual appearance, oxidative stability, methanol
residue, etc. [26]. After washing the crude biodiesel, the
methanol is removed from the mixture by either evapora-
tion (rotary evaporator) or distillation [69,75]. The moisture
content in the washed biodiesel is reduced by either heat-
ing or drying over sodium sulfate [41,51].
An interesting report cites the use of spent tea-
waste-derived activated carbon for purification, result-
ing in higher biodiesel yield and improved fuel proper-
ties as compared to the conventional purification
techniques. The spent activated carbon in this case
could be regenerated and reused [95].
The purification process yields a yellow-colored bio-
diesel liquid [13]. The biodiesel is analyzed for its fatty
acid methyl ester composition using gas chromatogra-
phy-mass spectrometry (GC-MS) [96]. Other techniques
such as high performance liquid chromatography
(HPLC), nuclear magnetic resonance sen utilized for
analysis [1,26,45,66,77,82]. Interestingly, laser spectros-
copy has been used to monitor the end point and
equilibrium state of the transesterification reaction
[97]. Hence, the time course of a reaction can be deter-
mined and used to optimize the yield and product pro-
file. The yield of biodiesel product obtained from an oil
sample is provided by Equation (3) [63,97]:
Biodiesel yield ð%Þ ¼
% Fame area from GCMS  Weight of product
 100 (3)
Weight of WCO Sample
The quality of biodiesel can be tested with the estab-
lished standard protocols such as European standard EN
14 214 and American standard ASTM D6751 [68,79]. The
European standard is more restrictive than the Ameri-
can standard [67]. The ASTM standards for biodiesel are
provided in Table 7 [4]. Biodiesel produced from any
method should essentially meet these standards.
Application of biodiesel as engine fuel
Biodiesel is identified as a potential alternative fuel for
compression ignition diesel engines as it could reduce
the use of fossil fuels and improve engine exhaust emis-
sions. Studies conducted by many researchers concluded
that as a motor fuel, biodiesel has certain benefits over
petroleum diesel [7,32,35,98]. Also, biodiesel with proper-
ties similar to that of petroleum diesel may be used in
engines without any modifications [25,35].
Biodiesel and petroleum diesel have been blended in
different proportions and their emission profile tested.
The emission profile shows that smoke, particulate mat-
ter, hydrocarbon (HC) and carbon monoxide (CO) emis-
sions decrease with increasing biodiesel concentration
in blends. But the NOx emissions increased with an
increase in biodiesel concentration in blends [23,35,93].
The reason for the increase in NOx emissions is due to
the increase in the combustion temperature and oxy-
gen content in the fuel [23]. It has been reported [11]
that B20 (biodiesel 20 v/v% and diesel 80 v/v%) pro-
duced from WCO resulted in significant reduction in
particulate matter, HC and CO emissions. Another report
states that with increasing biodiesel composition in the
blend, the density and viscosity increase, while the sul-
fur content was reduced in the fuel [32].
Conclusion
Biodiesel possesses properties similar to those of petro-
leum diesel and can be used in existing diesel
 8 A. R. MOHAMMED AND C. BANDARI
compression ignition (CI) engines without any modifi-
cations. It is a renewable fuel with many advantages
over petroleum diesel such as clean engine emissions,
biodegradability and low cost. WCO is a cost-effective
feedstock and can be transesterified to produce bio-
diesel. Homogeneous catalysts can be effective for oils
with low FFA content and can produce biodiesel of
high yield (more than 90 wt. %) at moderate reaction
conditions in relatively less time. These catalysts are
widely used for industrial applications. For feedstocks
containing high FFA content, esterification should be
done with an acid catalyst in order to reduce the FFA,
and this can be followed by transesterification using a
base catalyst. This two-step process prevents soap for-
mation and is widely employed in industrial produc-
tion. Some heterogeneous catalysts are very promising
as they can simultaneously perform esterification and
Downloaded by [Australian Catholic University] at 13:49 18 September 2017
transesterification to obtain high yields (up to 98 wt.
%) and can be recovered for reuse. However, a hetero-
geneous catalyst needs harsh reaction conditions.
Enzymes can catalyze with high yield but need a lon-
ger duration of reaction and are not economical. High
product yields also depend on the feedstock quality,
pretreatment and purification. The biodiesel produced
should meet quality standards prescribed by ASTM
D6751. B20, a blend of 20 v/v% biodiesel in petroleum
diesel, is ideal for diesel engines as it shows a signifi-
cant reduction in CO, HC and smoke emissions com-
pared to emissions from petroleum diesel.
Acknowledgements
We take this opportunity to convey our sincere gratitude to
Ramky Enviro Engineers Ltd, Hyderabad, India, for providing
full support and resources to complete this review. I would
also like to thank Mr. V Vijay Kumar, Ms. Swetha Nemmani,
Ms. Radhika Raghava, Ms. Bhargavi Radhakrishnan, Mr. Sub-
ash Koduri, Mr. Sarath Babu Reddy and Mr. Mayank Gupta for
their endless support for completion of this project.
Disclosure statement
No potential conflict of interest was reported by the authors.
ORCID
Abdul Raqeeb Mohammed http://orcid.org/0000-0003-
0689-700X
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