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Fuel 87 (2008) 2355–2373


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Review article

Advancements in development and characterization


of biodiesel: A review
Y.C. Sharma a,*, B. Singh a, S.N. Upadhyay b
a
Environmental Engineering and Research Laboratories, Department of Applied Chemistry, Institute of Technology, Banaras Hindu University,
Varanasi, UP 221 005, India
b
Department of Chemical Engineering and Technology, Institute of Technology, Banaras Hindu University, Varanasi, UP 221 005, India

Received 7 November 2007; received in revised form 21 January 2008; accepted 22 January 2008
Available online 20 February 2008

Abstract

An ever increasing demand of fuels has been a challenge for today’s scientific workers. The fossil fuel resources are dwindling day by
day. Biodiesel seems to be a solution for future. Biodiesel is an environmentally viable fuel. Out of the four ways viz. direct use and blend-
ing, micro-emulsions, thermal cracking and transesterification, most commonly used method is transesterification of vegetable oils, fats,
waste oils, etc. Latest aspects of development of biodiesel have been discussed in this work. Yield of biodiesel is affected by molar ratio,
moisture and water content, reaction temperature, stirring, specific gravity, etc. Biodegradability, kinetics involved in the process of bio-
diesel production, and its stability have been critically reviewed. Emissions and performance of biodiesel has also been reported.
Ó 2008 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Transesterification; Catalyst; Stability; Biodegradation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2356
1.1. Various raw materials used as feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2357
2. Production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
2.1. Acid esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
2.2. Alkaline transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
3. A special reference to karanja . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2362
4. Effect of different parameters on production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.1. Effect of molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.2. Effect of moisture and water content on the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.3. Effect of free fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.4. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.5. Effect of stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.6. Effect of specific gravity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
5. Biodegradability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
6. Stability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
7. Kinetics of the reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366
8. Diesel engine emissions and performance of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366

*
Corresponding author. Tel.: +91 542 2307025 (O), +91 9935616119 (M); fax: +91 542 2316428.
E-mail address: y_sharma_2002@rediffmail.com (Y.C. Sharma).

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.01.014
2356 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

9. Indian scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368


10. Cost of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368
11. Instrumentation involved in biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
12. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370

1. Introduction the conversion of monoglycerides to glycerol. In each step


an ester is produced and thus three ester molecules are pro-
Whenever I think of fuel, a picture of villages of devel- duced from one molecule of triglyceride [3]. Out of these
oping nations eclipsed in darkness, full of poverty, no three methods, transesterification is the most viable process
planned mechanization, agriculture depending on rain adopted known so far for the lowering of viscosity. It also
God for irrigation comes before my eyes. Be it lighting gives glycerol as a by-product which has a commercial
the house, agriculture, or cooking, each process requires value.
energy. Energy, most countries do not have energy even Stoichiometrically, three moles of alcohol are required
to light the cities! Superconductivity and hydrogen energy for each mole of triglyceride, but in general, a higher molar
reflected some promise but these were completely short- ratio is often employed for maximum ester production
lived. Biodiesel, yes, probably biodiesel is the FUEL of depending upon the type of feedstock, amount of catalyst,
future. temperature, etc. Commonly used alcohols include metha-
Biodiesel is derived from vegetable oils and hence is a nol, ethanol, propanol and butanol. However, the yield of
renewable fuel. Gasoline and diesel come in the category biodiesel is independent of the type of the alcohol used and
of non-renewable fuel and will last for a limited period of the selection of one of these depends on cost and perfor-
time. These non-renewable fuels also emit pollutants in mance. Methanol is preferred over others due to its low
the form of oxides of nitrogen, oxides of sulphur, carbon cost [1]. The conventional catalysts used are acid and alkali
dioxide, carbon monoxide, lead, hydrocarbons, etc. during catalysts depending upon the nature of the oil used for bio-
their processing and use. A renewable fuel such as biodie- diesel production. Another catalyst being studied is lipase.
sel, with lesser exhaust emissions, is the need of the day. Lipase has advantage over acid and alkali catalysts but its
Hence, researchers and scientific community worldwide cost is a limiting factor for its use in large scale production
have focused on development of biodiesel and the optimi- of biodiesel. Choice of acid and alkali catalysts depends on
zation of the processes to meet the standards and specifica- the free fatty acids (FFA) content in the raw oil. FFA
tions needed for the fuel to be used commercially without should not exceed a certain amount for transesterification
compromising on the durability of engine parts. The inter- to occur by an alkali catalyst. Invariably, on all aspects
est in the use of renewable fuel started with the direct use of of development of biodiesel, Ma and Hanna [4] have done
vegetable oils as a substitute for diesel. However, their significant work. Canakci and Van Gerpan [5,6] reported
direct use in compression ignition engines was restricted that transesterification was not feasible if FFA content in
due to high viscosity which resulted in poor fuel atomiza- the oil was about 3%. Ramadhas et al. [1] and Veljkovic
tion, incomplete combustion and carbon deposition on et al. [7] used rubber seed oil and tobacco seed oil, respec-
the injector and the valve seats causing serious engine foul- tively, with higher free fatty acid content (17%). The
ing [1]. Other constraints of the direct application of vege- authors reduced the FFA value to more than 2.0%, which
table oil were its low volatility and polyunsaturated corresponds to 4.0 mg KOH/g, by acid esterification using
character. To overcome these constraints, the processes like H2SO4 as a catalyst. Sahoo et al. [8] used zero catalyzed
pyrolysis, micro-emulsification, transesterification, etc. transesterification (using toluene) and acid esterification
were especially developed. Pyrolysis of the vegetable oil (using H2SO4) prior to alkaline esterification to reduce
resulted in products with low viscosity, high cetane num- the acid value from 22.0% to 2.0%. Sharma and Singh [3]
ber, accepted amounts of sulphur, water and sediments, also favored acid esterification prior to alkaline transesteri-
accepted copper corrosion values but were unacceptable fication with karanja oil as feedstock having FFA of 2.53%
in the terms of their ash contents, carbon residues, and (5.06 mg KOH/g) using H2SO4. In the same manner, the
pour points. Similarly, micro-emulsion of vegetable oil acid value of jatropha which corresponds to 14% FFA
lowered the viscosity of the oil but resulted in irregular was reduced to less than 1% by using H2SO4 [9]. Table 1
injector needle sticking, heavy carbon deposits and incom- depicts the values of initial FFA of the feedstock, the level
plete combustion during 200 h laboratory screening endur- reached after acid esterification and the amount of H2SO4
ance test [2]. Transesterification is a chemical reaction used. After treatment with acid catalyst, H2SO4, the free
between triglyceride and alcohol in the presence of a cata- fatty acid (FFA) value is reduced to less than 2.0% to make
lyst. It consists of a sequence of three consecutive reversible transesterification reaction feasible. Table 2 depicts the
reactions where triglycerides are converted to diglycerides, yield/conversion of biodiesel with different oils taken.
diglycerides are converted to monoglycerides followed by The yield of biodiesel ranged from 56% from Chlorella
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2357

Table 1
Values of initial FFA content of different feedstock
Feedstock Initial FFA (%) FFA after treatment (%) Amount (%) and catalyst used Reference
Rubber oil 17.0 <2.0 0.5, H2SO4 [1]
Karanja oil 2.53 0.95 0.5, H2SO4 [3]
Tobacco oil 35.0 <2.0 1.0/2.0, H2SO4 [7]
Polanga oil 22.0 <2.0 0.65, H2SO4 [8]
Jatropha oil 14.0 <1.0 1.43, H2SO4 [9]
Mahua oil 19.0 <1.0 1.0, H2SO4 [10]
Karanja oil 2.53 0.3 KOH (appropriate amount) [11]
– 37.96 ± 0.018 1.05 ± 0.018 2.0 Fe2SO4 [16]
– 40.0 <1.0 – [18]

Table 2 higher molar ratio (7:1, methanol/UFO), and more amount


Yield of biodiesel with different feedstock of catalyst (1.1 wt% NaOH) was needed when compared to
Oil taken for study Yield Conversion Reference edible canola oil where optimal conditions were 315–
(%) (%) 318 K, 6:1 methanol/oil molar ratio and 1.0 wt% NaOH.
Karanja (Pongamia pinnata) 89.5 – [3] However, comparatively a less time (20 min) was needed
Tobacco (Nicotina tabacum) 91 – [7] in UFO for completion of reaction in comparison to canola
Polanga (Calophyllum inophyllum) – 85 [8] oil where reaction time took 60 min. Non-edible oils used
Jatropha (Jatropha curcas) 99 – [9]
Mahua (Madhuca indica) 98 – [10]
for transesterification mostly are the oils with higher free
Karanja (Pongamia pinnata) 97–98 – [11] fatty acids such as rubber (Ficus elastica), jatropha (J. cur-
Karanja (Pongamia pinnata) – 92/95 [14] cas), karanja (Pongamia pinnata), mahua (Madhuca indica),
Soybean (Glycine max) – 98.4 [15] polanga (Calophyllum inophyllum), tobacco (Nicotina taba-
Waste cooking oil 97.02 – [16] cum), etc. In an attempt to reduce the cost of biodiesel, mic-
Canola oil (Brassica napus) 90.04 98 [19]
Used frying oil 87.5 94 [19]
roalgal oils have also been tried by researchers as a source
Sunflower oil (Helianthus annuus) – Nearly [20] of feedstock for the production of biodiesel due to their
complete higher photosynthetic efficiency, higher biomass produc-
Chlorella protothecoides 56 – [21] tion and faster growth as compared to other energy crops
Chlorella protothecoides – >80 [22] [32–35]. Miao and Wu [21] reported production of biodie-
sel from microalga C. protothecoides using 100% catalyst
quantity (based on oil weight) with 56:1 molar ratio of
protothecoides to 99% from Jatropha curcas. The conver-
methanol to oil at temperature of 303 K in 4 h of reaction
sion of biodiesel ranged from more than 80% from
time. The specific gravity of biodiesel produced reduced
C. prothecoides to 98.4% from soybean oil.
from initial value of 0.91 to a final value of 0.86. Xu
Various oils have been in use in different countries as
et al. [22] obtained high quality and low cost biodiesel from
raw materials for biodiesel production owing to its avail-
microalgae C. protothecoides of heating value 41 MJ kg1,
ability. Soybean oil is commonly used in United States density 0.864 kg L1 and viscosity 5.2  104 Pa S at
and rapeseed oil is used in many European countries for 313 K. C. protothecoides have earlier been reported as a
biodiesel production, whereas, coconut oil and palm oils feedstock for aquaculture feeds, human food supplements
are used in Malaysia for biodiesel production [10–13].
and pharmaceuticals [36–39].
Transesterification of edible oils has also been carried out
Attributing to its low cost, waste cooking oil has also
from the oil of canola and sunflower. Other edible and
been tried by researchers to develop biodiesel. The idea
non-edible oils, animal fats, algae and waste cooking oils
comes from the fact that triglycerides comprise of greases
have also been investigated by researchers for the develop-
and oil. Oils are generally in liquid state at room tempera-
ment of biodiesel [14–31]. Table 3 depicts the work carried ture, whereas greases and fats are in solid state at room
out for biodiesel production from various feedstocks under temperature. Recycled grease is termed as waste grease
different conditions. Type and amount of variables such as and is classified as yellow and brown grease depending
feedstock, alcohol, molar ratio, catalyst, reaction tempera-
on free fatty acid composition [17]. The price of yellow
ture, time duration, rate and mode of stirring affects the
grease (FFA < 15%) ranges from $0.04 to $0.09 kg1 while
yield and conversion of biodiesel.
the price of brown grease (FFA > 15%) ranges between
0.004 and $0.014 kg1 [40]. Biodiesel development from
grease can reduce its production cost. In United States,
1.1. Various raw materials used as feedstock
an estimate reveals that biodiesel production from 5.2 bil-
lion kg/year of greases and animal fats could replace 1.5
Leung and Guo [19] compared the transesterification
million gallons of diesel fuel. The major constraint of direct
reaction conditions of neat canola oil with used frying oil
application of waste frying oil lies in its higher amount of
(UFO). A comparatively higher temperature (333 K),
2358
Table 3
Biodiesel production from different feedstock
Year Feedstock Transesterification Alcohol Molar Catalyst Reaction Duration Stirring Conversion/yield Reference
Ref stages ratio temperature

Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373


(methanol (K)
to oil)
2004 Sunflower oil Single step Supercritical 40:1 No catalyst 473–673 10– – 78–96% [20]
methanol (pressure 40 min conversion with
Supercritical 200 bar) increase in
ethanol temperature
Methanol 5:1 Supercritical 318 6h 23% conversion
Ethanol CO2 + lipase (Novozym 27% conversion
435) 30 wt% of oil
2005 Pongamia pinnata Single step Methanol 10:1 KOH (1% by wt) 378 1.5 h – 92% conversion [14]
ZnO 83% conversion
Hb-Zeolite 393 24 h 59% conversion
Montmorillonite 47% conversion
2005 Madhuca indica Two step Methanol 0.30–0.35 1% v/v H2SO4 333 1h – 98% yield [10]
v/v
0.25 v/v 0.7% w/v KOH – 1h –
2005 Rubber seed oil Two step Methanol 6:1 H2SO4 0.5% by volume 318 ± 5 20– Magnetic stirrer – [1]
30 min
9:1 NaOH 0.5% by volume 318 ± 5 30 min
2006 Chlorella Methanol 56:1 Acid catalyst 303 More than 80% [22]
protothecoides conversion
2006 Chlorella Methanol 56:1 H2SO4 (100%) on the 303 4h – 63% yield [21]
protothecoides basis of oil weight
2006 Neat canola oil Single step Methanol 6:1 NaOH 1.0 wt% 318 15 min Magnetic stirring 1100 rpm in Ester content [19]
the first stage (10 min) and 98 wt%
Used frying oil 7:1 NaOH 1.1 wt% 333 20 min 600 rpm in second stage Ester content
94.6 wt%
2006 Nicotiana Two step Methanol 18:1 H2SO4 (1% with lower 333.0 ± 0.1 25 min Magnetic stirrer 400 rpm Yield 91% in [7]
tabacum L. molar ratio) (2% with 30 min
(tobacco) higher molar ratio)
6:1 KOH (1% based on the 30 min
oil wt.)
2006 Pongamia pinnata Single step Methanol 6:1 KOH (1% by weight) 338 2h Mechanical stirrer 360 rpnm Yield 97–98% [11]
12:1 1h
2006 Soybean oil Methanol 4.5:1 TiO2/ZrO2 (11 wt% Ti) 448 2h Conversion over [23]
Al2O3/ZrO2 (2.6 wt% Al) 95%
K2O/ZrO2 (3.3 wt% K) Conversion 100%
2006 Monosodium Two step Methanol 0.5 M 1 ml KOH (0.5 M) 333 10 min – Yield [24]
glutamate 12.5%, v/v 1 ml BF3 (12.5%, v/v) 353 5 min 92.54 ± 2.00%
wastewater
2006 Soybean oil Single step alkali Methanol 6:1 NaOH 318 10– Mechanical stirrer 900 rpm Yield 100% [25]
catalyzed 20 min Power ultrasonic (frequency
19.7 KHz, power 150 W)
Hydrodynamic cavitation
(operation pressure 0.7 MPa)
2007 Jatropha, Single step Methanol 3:1 NaOH/KOH (1 wt% of – 2–4 h Stirring – [12]
pongamia, oil)
sunflower,
soybean, palm
2007 Calophyllum Three step zero Methanol 6:1 Anhydrous H2SO4 338 2h Mechanical stirring 450 rpm 85% yield in [8]

Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373


inophyllum catalysed (98.4%) 0.65% by volume 90 min
Acid catalysed 4h Complete in 4 h
Alkali catalysed 9:1 KOH 1.5% by weight 4h reaction
2007 Jatropha curcas Two step acid Methanol 0.28 v/v H2SO4 1.43% v/v 333 88 min >99% yield [9]
catalysed (3.5 + acid value, w/v
KOH)
Alkali catalysed 0.16 v/v 24 min
2007 Triolein Single step Ethanol 10:1 Anion exchange resin 323 60 min – 98.8% purity [26]
Cation exchange resin
(heterogeneous catalyst)
2007 Sunflower oil Single step Methanol 13:1 Activated CaO (1 wt%) 333 100 min Helix stirrer 1000 rpm – [27]
2007 Waste cooking oil Two step Methanol 10:1 Fe2SO4 368 4h No stirring because boiling was 97.02% conversion [16]
6:1 KOH 338 1h sufficient
2007 Karanja Two step Methanol 8:1 H2SO4 318 ± 2 30 min Magnetic/mechanical 89.5% yield with [3]
mechanical
9:1 NaOH/KOH 30 min 85% yield with
magnetic

2359
2360 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

Fig. 1. Basic scheme for biodiesel production.

FFA. The FFA level of fresh soybean oil has been reported be less than 4.0 mg KOH/g [1,3]. The commonly used cat-
to change from 0.04% to 1.51% after 70 h of frying at alyst during acid esterification of neat oil is sulphuric acid
463 K [41]. Hence, due to higher FFA, direct conversion (H2SO4) [1,3,7–10]. Nevertheless, this process too has a
of waste restaurant oil and animal fats to biodiesel via drawback as water is produced along with ester from the
alkaline catalyst is not possible. The level of FFA, there- reaction of FFA with alcohol which inhibits the transeste-
fore, is reduced by an acid catalyst. rification of glycerides [17]. For waste cooking oil too the
Following this advantage, researchers have advocated acid employed is sulphuric acid [29–31]. But in this case,
the use of rendered animal fats and restaurant waste oils the conversion reported is low (82%) and the alcohol
as biodiesel feedstocks [18,42–47]. A major limiting factor required for the reaction is high (200% excess of ethanol)
of biodiesel is its inverse relationship between its oxidation [16]. Wang et al. [16] have, therefore, tried a new catalyst
stability and its cold flow properties. Saturated compounds Fe2(SO4)3 (ferric sulphate) as an alternate to sulphuric acid
have good oxidation stability but poor cold temperature and have reported much better conversion (97.02%). As,
properties. Unsaturated compounds have better low tem- ferric sulphate is insoluble in oil, it was centrifuged from
perature properties but fail in oxidation stability [12,17]. the liquid after acid esterification and reused for the next
Here, the waste oil product can be of advantage over the batch. High temperature and high concentration of
neat vegetable oil as they have a higher proportion of sat- H2SO4 as catalyst could burn some of the oil which will
urated fatty acids [17] and hence can provide better oxida- then cause low yield of biodiesel product.
tive stability. Wang et al. [16] have achieved 97.02% yield of
biodiesel from waste cooking oil of high acid value i.e. 2.2. Alkaline transesterification
75.92 ± 0.036 mg KOH/g, by a two step catalysis process.
A novel method has been developed by Xue et al. [24] For oil samples with FFA below 2.0%, alkaline transe-
for the production of biodiesel from monosodium gluta- sterification is preferred over the acid catalyzed transesteri-
mate wastewater having COD of 10,000 mg/L. After treat- fication as the former is reported to proceed about 4000
ment the COD removal was 85% with 10% formation of times faster than the latter [2]. The common catalyst
crude lipid. The crude lipid was biosynthesized by rhodo- employed during alkaline transesterification at industrial
torula glutinis by transesterification reaction with methyl level application includes the homogeneous catalysts
ester yield of 92.54 ± 2.0%. Biodiesel has also been synthe- sodium hydroxide, potassium hydroxide, etc.
sized using triolein as a feedstock [26]. Fig. 1 depicts the The use of homogeneous catalyst such as sodium
basic scheme for biodiesel production [48]. hydroxide and potassium hydroxide has been successful
at industrial level for production of biodiesel. However,
2. Production of biodiesel the biodiesel and glycerin produced have to be purified to
remove the basic catalyst and need its separation by wash-
2.1. Acid esterification ing with hot distilled water twice or thrice. Thus, heteroge-
neous catalyst has also been tried by researchers to
The acid value is a measure of the number of acidic overcome this drawback of time consumption and colossal
functional groups in a sample and is measured in terms consumption of water. The heterogeneous catalyst can be
of the quantity of potassium hydroxide required to neutral- separated from the final product by filtration which checks
ize the sample. Acid value of the feedstock for alkaline time consumption and prevents the consumption of large
transesterification has to be reduced to less than 2.0 mg volume of water. The filtered solid then can be reused.
KOH/g [15,49–51]. However, other authors advocate it to The application of a heterogeneous catalyst, CaO has been
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2361

tested by Grandos et al. for its feasibility [27]. The experi- (2.0 kg) as an alkaline catalyst for transesterification.
ments confirmed that CaO could be used as a catalyat for Sahoo et al. [8] used alkaline transesterification after reduc-
the transesterification reaction without significant deactiva- ing the free fatty acid value from 44 mg KOH/g (i.e. 22%)
tion up to eight runs with significant amount of CaO. to less than 4 mg KOH/g (i.e. <2%) through zero catalyzed
Leung and Guo [19] tried three different homogeneous and acid catalyzed transesterification. 1.5% by weight of
catalysts i.e. sodium hydroxide (NaOH), potassium potassium hydroxide was found sufficient for the maximum
hydroxide (KOH), and sodium methoxide (CH3ONa). yield of ester. Sarin et al. [12] prepared a series of biodiesel
The optimum requirement of the catalyst were 1.1, 1.3 from the edible oils such as sunflower, soybean, palm and
and 1.5 wt% for NaOH, CH3ONa, and KOH respectively non-edible oils such as jatropha and karanja. The catalyst
for the maximum ester content. The amount of NaOH used was either NaOH or KOH with 1 wt % of oil.
required was less than the amounts of both the CH3ONa The amount of alkali catalyst was calculated on the
or KOH for the same conversion of fatty acid methyl ester basis of the amount needed to neutralize the unreacted
as NaOH has lower molar mass (40 g/mol), compared to acids plus 0.35% for virgin oil which came out to be
CH3ONa (54 g/mol) and KOH (56 g/mol). 0.55% w/v KOH [9]. 1.0% KOH was reported as the opti-
However, in terms of yield, CH3ONa proved to be a bet- mal amount for alkaline transesterification reaction of
ter catalyst than NaOH and KOH because CH3ONa disso- karanja oil by Meher et al. [11] and Karmee and Chadha
ciates into CH3 O and Na+ and does not form any water [14]. Karmee and Chadha also tried Hb-Zeolite, montmo-
as side product. On the other hand, NaOH and KOH rillonite K-10 and ZnO but the conversion of fatty acid
forms sodium (or potassium) methoxide when dissolved methyl ester was less. Around 83% conversion with ZnO
in methanol and produces water. This water then reacts was possible only with a longer reaction time of 24 h. Even
with Na+ (or K+) to form sodium (or potassium) soaps. lesser conversions of 59% and 47% were achieved with Hb-
Potassium methoxide (KOCH3) has also been used as an Zeolite and montmorillonite K-10, respectively, in compar-
alkali catalyst by dissolving potassium hydroxide in meth- ison to 92% achieved by KOH.
anol [52]. Sharma and Singh [3] reported better yield with While using the refined karanja oil, the conversion
NaOH as a catalyst over KOH while using magnetic stir- reached to 99% with 0.5% of NaOH or CH3ONa [14].
rer. Whereas, when mechanical stirrer was adopted the 1% KOH was optimum amount of catalyst even with used
yield was same with equal amount of NaOH and KOH frying oil reported by Marinkovic and Tomasevic [55].
(0.5 wt%). However, during the separation of the final Ghadge and Raheman [10] calculated the amount of cata-
products from glycerol, KOH was more convenient. Potas- lyst to be 0.7% w/v KOH as the cumulative sum of 0.5% for
sium soaps being softer than sodium soaps did not block catalyst plus the amount needed to neutralize the unreacted
the bottom of separating funnel unlike latter and were acids (2 mg KOH/g) i.e. 0.2%. NaOH was used as a cata-
removed easily. Hence, KOH as catalyst is preferred over lyst by Ji et al. [25] with power ultrasonic and hydrody-
NaOH at industrial level application [3,19]. namic cavitation methods and found the methods
The base catalyzed reaction is reported to be very sensi- superior as compared to mechanical stirring. The amount
tive to the purity of the reactant. FFA content should not of KOH used for the transesterification of tobacco (Nicoti-
exceed beyond a certain limit. The efficiency of the reaction ana tabacum) oil after acid esterification as reported by Vel-
was affected to some extent when FFA content exceeded jkovic et al. [7] is 1.0% (based on oil weight) with a yield of
0.5 wt% [28]. However, when the feedstock is waste cook- 91%. Using the same oil Usta got a yield of 86%. Hence,
ing oil, the limit of FFA is a bit relaxed and FFA content the two step process of acid and alkaline esterification
a little beyond 1.0 wt% did not have any effect on the can be expected to yield a better result when compared to
methyl ester conversion [16,53]. The amount of catalyst one step base catalyzed transesterification [56]. In an
(KOH) required was 1.0 wt% to reach 97.02% conversion attempt to find a new catalyst, Furuta et al. [23] tested
of biodiesel. amorphous zirconia solid catalysts, TiO2/ZrO2 (11 wt%
Ramadhas et al. [1] have reduced the acid value to less Ti) and Al2O3/ZrO2 (2.6 wt% of Al) and reported more
than 2.0% through acid catalyst followed by alkaline than 95% conversion. The reason for this is the amphoteric
transesterification. The amount of catalyst used for alka- nature of zirconia. However, the temperature required was
line transesterification ranged between 0.3% and 1.0%. quite high i.e. 448–473 K.
The maximum conversion efficiency was reported at 0.5% The homogeneous catalysts require neutralization and
of NaOH during alkaline transesterification. Excess separation steps from the reaction mixture. To accomplish
amount of catalyst gave rise to formation of an emulsion. this, water, solvents and energy are needed. To overcome
This increased the viscosity and led to the formation of these, heterogeneous based catalysts have been tested by
gels. Conversion efficiency decreased to 60% when the cat- researchers, where separation is possible without using
alyst amount was increased to 0.8% (wt of NaOH/wt of solvent and shows easy regeneration. The nature of the
oil). However, esterification also did not take place without final product has been less corrosive in character and the
sufficient amount of the catalyst. whole process is termed safer, cheaper and more environ-
Srivastava and Verma [54] used sodium methoxide solu- ment friendly [57]. The heterogeneous catalyst being used
tion prepared by dissolving NaOH (28.5 g) and methanol by researchers include alkaline–earth oxides, zeolites,
2362 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

hydrotalcites, MgO and CaO [27,57–62]. In addition, reac- as the solubility parameter of ethanol is closer to the solu-
tor heating was not needed when MgO was used as a cat- bility parameter of the oil. But, high temperature and high
alyst in batch process [57]. pressure conditions i.e. 573 K and 20 MPa are needed for
Another method where neither acid nor base catalyst is the reaction to proceed and complete. [13,20]. Another
required is non-catalytic transesterification where super- added advantage with heterogeneous based catalyst is the
critical methanol is used instead of methanol and nearly lesser consumption of catalyst. As per the study by Zhang
complete conversion is achieved. The reason is that, the et al. [29] annually 88 tonnes of sodium hydroxide is
oil and supercritical methanol exist in the single phase needed for 8000 tonnes of biodiesel production. While as
[20,63–67]. The advantage with supercritical methanol is per the simulation study by Dossin et al. [57] the require-
that the conversion gets 95% complete in 10 min. But at ment of MgO will be only 5.7 tonnes for 100,000 tonnes
the same time, higher molar ratio (40:1) is employed. The production of biodiesel.
supercritical condition is based on the effect of relationship
between pressure and temperature upon the thermophysi- 3. A special reference to karanja
cal properties of the solvent, such as dielectric constant,
viscosity, specific weight and polarity. There is a decrease Among the several indigenous plant species, karanja is
in the dielectric constant of methanol in supercritical state. one of the medium sized plants found in several parts of
Fig. 2 depicts the influence of temperature and alcohol used India. The plant is also said to be highly tolerant to salinity
in the synthesis of biodiesel. In methanol, conversion and is reported to be grown in various soil textures viz.
increased from 78% to 96% with increase in temperature. stony, sandy and clayey. Karanja can grow in humid as
The conversion was even higher with supercritical ethanol well as subtropical environments with annual rainfall rang-
ing between 500 and 2500 mm. This is one of the reasons
for wide availability of this plant species. The constituents
of karanja oil viz. furanoflavones, furanoflavonols, chro-
menoflavones, flavones and furanodiketones make the oil
non-edible and hence the oil is underutilized. The presence
of these constituents, however, gives the oil antifungal
characteristics and enhances its application in medicinal
ointments. The woody part of the tree is still in use by tri-
bal people where the plant is locally available such as
brushing of teeth. The oil expelled from the seeds is also
burned during the festival of lighting to purify the environ-
ment. All these applications are at local or regional level
and 94% of the oil from plant is still underutilized. The
present production of karanja oil approximately is 200 mil-
lion tons per annum [11]. However, its production poten-
tial is much more i.e. 135,000 million tones per annum
[8]. The time needed by the tree to mature ranges from 4
to 7 years and depending on the size of the tree the yield
of kernels per tree is between 8 and 24 kg. The oil content
extracted by various authors ranges between 30.0 to 33%
[3,14]. The oil is used by common people due to its low cost
and easy availability. The fatty acid composition of karanja
oil has been reported in Table 4. Karanja oil comprises of

Table 4
Different fatty acids present in karanja oil [107]
Fatty acid Systematic name Formula Structure wt%
(common
name)
Palmitic Hexadecanoic C16H32O2 16:0 10.6
Stearic Octadecanoic C18H36O2 18:0 6.8
Oleic cis-9-octadecenoic C18H34O2 18:1 49.4
Linoleic cis-9, cis-12-octadecadienoic C18H32O2 18:2 19.0
Arachidic Eicosanoic C20H40O2 20:0 4.1
Gadoleic 11-eicosenoic C20H38O2 20:1 2.4
Fig. 2. Synthesis of biodiesel at various temperatures in supercritical (a)
Behenic Docosanoic C22H44O2 22:0 5.3
methanol, (b) ethanol (j) 473 K, () 523 K, (N) 573 K, (.) 623 K, ()
Lignoceric Tetracosanoic C24H48O2 24:0 2.4
673 K.
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2363

Table 5
Test method and limits of biodiesel along with its comparison with karanja oil methyl ester [12]
Property (units) ASTM 6751 test method ASTM 6751 limits IS 15607 test method IS 15607 limits Karanja oil methyl ester
Flash point (°C) D-93 Min. 130 IS 1448 P:21 Min. 120 141
Viscosity at 40 °C (cSt) D-445 1.9–6.0 IS 1448 P:25 2.5–6.0 4.16
Sulphated ash (mass%) D-874 Max. 0.02 IS 1448 P:4 Max. 0.02 0.002
Sulphur (mass%) D-5453 Max. 0.05 ASTM D 5453 Max. 0.005 0.003
Cloud point (°C) D-2500 NA IS 1448 P:10 NA 4
Copper corrosion D-130 Max. 3 IS 1448 P:15 Max. 1 1
Cetane number D-613 Min. 47 IS 1448 P:9 Min. 51 55.1
Water and sediment (vol. %) D-2709 Max. 0.05 D-2709 Max. 0.05 0.03
CCR 100% (mass%) D-4530 Max. 0.05 D-4530 Max. 0.05 <0.01
Neutralization value (mg, KOH/gm) D-664 Max. 0.80 IS 1448 P:1/Sec. 1 Max. 0.50 0.10
Free glycerin (mass%) D-6584 Max. 0.02 D-6584 Max. 0.02 0.01
Total glycerin (mass%) D-6584 Max. 0.24 D-6584 Max. 0.25 0.01
Phosphorus (mass%) D-4951 Max. 0.001 D-4951 Max. 0.001 <0.001
Distillation temperature D-1160 90% at 360 °C Not under spec. – 90%
Oxidation stability, h NA NA EN 14112 Min. 6 h 2.35

29.2% saturated fatty acids and 70.8% unsaturated fatty Singh [3] used similar two step transesterification and took
acids. The maximum proportion comprises of oleic acid 8:1 molar ratio for acid esterification and 9:1 molar ratio
(cis-9-octadecenoic) i.e. 49.4%, whereas, gadoleic acid for alkaline esterification for optimum yield of biodiesel
(11-eicosenoic, 2.4%) and linoceric acid (tetracosanoic, production from karanja oil. Veljkovic et al. [7] used 18:1
2.4%) are in traces. Table 5 depicts the ASTM 6751 and molar ratio during acid esterification and 6:1 molar ratio
IS 15607 test methods and limits for biodiesel. In respect during alkaline esterification. Meher et al. [11] carried out
of karanja, it is observed that it meets all the specification investigation with 6:1 molar ratio during acid esterification
of American Society for Testing and Materials (ASTM) and 12:1 molar ratio during alkaline esterification. Instead
and Indian Standards but fails in oxidation stability test. of taking molar ratio, Tiwary et al.[9] and Ghadge and
Hence, appropriate methods have to be devised to make Raheman [10] used volume as a measure of ratio. While
the karanja oil methyl ester fit for commercialization. Tiwary et al. used 0.28 v/v (methanol/oil) during acid
For the transesterification reaction, Sharma and Singh esterification and 0.16 v/v (methanol/oil) during alkaline
[3] advocated for 8:1 molar ratio during acidic esterification esterification, Ghadge and Raheman used 0.30–0.35 v/v
so as to reduce the acid value below 2 mg KOH/g i.e. 1.0% (methanol/oil) during acid esterification and 0.25 v/v
FFA. For the alkaline transesterification reaction, the (methanol/oil) during alkaline esterification. Karmee and
authors advocate 9:1 molar ratio for the completion of Chadha [14] used a single step transesterification and
the reaction. Mechanical stirrer produced better results have achieved 92% conversion by taking 10:1 molar
than magnetic stirrer and resulted in higher yield (89.5%) ratio.
in 1 h with 0.5% H2SO4 and 0.5% NaOH at 318 ± 2 K. Presence of sufficient amount of methanol during the
Meher et al. [11] have neutralized the oil by using potas- transesterification reaction is essential to break the glycer-
sium hydroxide to reduce the acid value of the oil from ine-fatty acid linkages [68]. But excess of methanol should
5.06 mg KOH/g to 0.6 mg KOH/g. The yield of 97.0– be avoided. Increasing the molar ratio of methanol/oil
98.0% was achieved in 2 h with 6:1 molar ratio (metha- beyond 6:1 neither increases the product yield nor the ester
nol:oil); and in 1 h with 12:1 molar ratio. The optimum content, but rather makes the ester recovery process com-
temperature was 338 K with the rate of stirring 360 rpm plicated and raised its cost. Leung and Guo [19] suggested
and 1% KOH as catalyst. Karmee and Chadha [14] have that methanol has polar hydroxyl group which can act as
reported 92% conversion with karanja oil using 10:1 an emulsifier causing emulsification. Thus separation of
molar ratio (methanol:oil) at 333 K with 1.0% KOH by the ester layer from the water layer becomes difficult. Miao
weight. and Wu [21] have reported that addition of large quantity
of methanol, i.e. 70:1 and 84:1 molar ratio slowed down the
separation of the ester and glycerol phases during the pro-
4. Effect of different parameters on production of biodiesel
duction of biodiesel. 56:1 molar ratio was reported to be
optimum for transesterification of microalgal oil.
4.1. Effect of molar ratio

Ramadhas et al. [1] and Sahoo et al. [8] reported 6:1 4.2. Effect of moisture and water content on the yield of
molar ratio during acid esterification and 9:1 molar ratio biodiesel
(alcohol:oil) during alkaline esterification to be the opti-
mum amount for biodiesel production from high FFA rub- Kusdiana and Saka [69] observed that water could
ber seed oil and polanga seed oil respectively. Sharma and pose a greater negative effect than presence of free fatty
2364 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

Fig. 3. Plots for yields of methyl esters as a function of water content in Fig. 4. Effect of FFA on the yield of methyl ester during alkali catalyzed
transesterification of triglycerides. transesterification.

4.4. Effect of temperature


acids and hence the feedstock should be water free.
Romano [70] and Canakci and Van Gerpen [5] insisted The temperature maintained by the researchers during
that even a small amount of water (0.1%) in the transeste- different steps range between 318 and 338 K. The boiling
rification reaction would decrease the ester conversion point of methanol is 333.7 K. Temperature higher than this
from vegetable oil. Demirbas [13] too reported a decrease will burn the alcohol and will result in much lesser yield. A
in yield of the alkyl ester due to presence of water and study by Leung and Guo [19] showed that temperature
FFA as they cause soap formation, consume catalyst higher than 323 K had a negative impact on the product
and reduce the effectiveness of catalyst. Srivastava and yield for neat oil, but had a positive effect for waste oil with
Verma [54] removed the moisture content from the vege- higher viscosities.
table oil by heating in oven for 1 h at 383 K. Meher et al.
[11] too reported a precautionary step to prevent moisture
absorbance and maintenance of catalytic activity by pre- 4.5. Effect of stirring
paring the fresh solution of potassium hydroxide and
methanol. Ellis et al. [52] found that even a small amount Stirring can play an important role in the yield of biodie-
of water in the feedstock or from esterification reaction sel production. Meher et al. [11] conducted the transesteri-
producing water from FFA might cause reduction in con- fication reaction with 180, 360 and 600 revolutions per
version of fatty acid methyl ester and formation of soap minute (rpm) and reported incomplete reaction with
instead. At the same time the presence of water had a 180 rpm. The yield of methyl ester was same with 360
positive effect in the yield of methyl esters when methanol
at room temperature was substituted by supercritical
methanol. However, no explanation for this has been pro-
vided. [13]. Fig. 3 depicts the influence of water content
on yield of methyl esters. It is observed that acid catalyst
is most prone to presence of water followed by alkaline
catalyst. No effect on ester content was observed when
supercritical methanol was used. The presence of water
had negligible effect on the conversion while using lipase
as a catalyst [20,71].

4.3. Effect of free fatty acids

Free fatty acids (FFAs) content after acid esterification


should be minimal or otherwise less than 2% FFAs. These
FFAs react with the alkaline catalyst to produce soaps
instead of esters. Fig. 4 depicts the effect of FFAs on the
yield of methyl ester during alkali catalysed transesterifica- Fig. 5. The variation of product specific gravity with reaction time under
tion. There is a significant drop in the ester conversion different molar ratio of methanol to oil. Reaction conditions: 303 K,
when the free fatty acids are beyond 2% [72]. 160 rpm, 100% catalyst quantity based on oil weight.
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2365

Table 6
Comparison of different technologies to produce biodiesel
Variable Alkali catalysis Lipase catalysis Supercritical alcohol Acid catalysis
Reaction temperature (K) 333–343 303–313 512–658 328–353
Free fatty acid in raw materials Sapanofied products Methyl esters Esters Esters
Water in raw materials Interference with reaction No influence – Interference with reaction
Yield of methyl esters Normal Higher Good Normal
Recovery of glycerol Difficult Easy – Difficult
Purification of methyl esters Repeated washing None – Repeated washing
Production cost of catalyst Cheap Relatively expensive Medium Cheap

and 600 rpm. Sharma and Singh [3] reported that mode of than 98% degradation of pure biodiesel after 28 days is
stirring too plays a vital role in the transesterification reac- reported by Pasqualino et al. [73] in comparison to 50%
tion. The yield of biodiesel increased from 85% to 89.5% and 56% by diesel fuel and gasoline respectively. Also,
when magnetic stirrer (1000 rpm) was replaced with the time taken to reach 50% biodegradation reduced from
mechanical stirrer (1100 rpm). A plausible explanation 28 to 22 days in 5% biodiesel mixture and from 28 to 16
may be a thorough mixing of the reactants by mechanical days in case of 20% biodiesel mixture at room temperature.
stirrer. The biodegradability of the mixture was reported to
increase with addition of biodiesel. Table 7 depicts the bio-
4.6. Effect of specific gravity degradability of fossil diesel under different conditions [77–
80].
Lower value of the specific gravity of the final product is
an indication of completion of reaction and removal of 6. Stability of biodiesel
heavy glycerine. The influence of molar ratio, temperature
and catalyst quantity on the specific gravity of the biodiesel Biodiesel, chemically is fatty acid methyl ester if alcohol
was studied by Miao and Wu [21]. The specific gravity of used during transesterification is methanol or fatty acid
the product decreased sharply up to 2 h of reaction time ethyl ester in case of ethanol. This ester molecule will get
using 30:1 molar ratio and up to 4 h of reaction time using hydrolyzed to alcohol and acid in the presence of air. Con-
45:1 and 56:1 molar ratio after which it was almost con- version of ester into alcohol will lead to reduction in flash
stant. The best process combination reduced the product point whereas conversion of ester into acid will increase the
specific gravity from 0.912 to 0.864 with 100% catalyst, total acid number. This makes the biodiesel unstable on
56:1 molar ratio at 303 K in 4 h of reaction time. Fig. 5 storage [12]. The stability of biodiesel also depends on
depicts the change in specific gravity with reaction time the feedstock used for the biodiesel production. The feed-
under different molar ratio of methanol to oil. A compari- stock with larger proportion of saturated fatty acids will
son of different technologies to produce biodiesel is shown be more stable than those having larger proportion of
in Table 6 [48]. unsaturated fatty acids. But again, higher portion of satu-
rated fatty acid lowers the low temperature properties such
as cloud and pour points. Hence, a major drawback of bio-
5. Biodegradability of biodiesel
diesel lies in its tradeoff between the level of saturation of
biodiesel and its cold flow properties [12,17]. The oxidation
Biodiesel is reported to be highly biodegradable in fresh-
stability of biodiesel is not dependent on the total number
water as well as soil environments. 90–98% of biodiesel is
of double bonds but on the total number of bis-allylic sites
mineralized in 21–28 days under aerobic as well as anaero-
(the methylene CH directly adjacent to the two double
bic conditions [73–75]. Biodiesel has been reported to
bonds). These esters undergo auto-oxidation which is
remove twice the amount of crude oil from sand as conven-
dependent on the number and position of the double bonds
tional shoreline cleaners [76]. Biodiesel increases the biode-
and forms by-product such as acids, esters, aldehydes,
gradability of crude oil by means of cometabolism. More
ketones, lactones, etc. [12,81–83].
Fatty acid methyl esters form a radical next to the dou-
Table 7
ble bond during the oxidation process. This radical binds
Biodegradability of fossil diesel with the oxygen in air, which is a biradical to form peroxide
% No. of Reference
radical. A new radical is created from the fatty acid methyl
degradation days ester by this peroxide radical which binds with oxygen in
Artificially contaminated soils 67 109 [77]
air. This augments the auto-oxidation cycle at an exponen-
Using soil columns 81 310 [78] tial rapid rate whereby 100 new radicals are created quickly
Fuel contaminated soil in the arctic 90–95 365 [79] from one single radical resulting in the formation of a series
Under aerobic conditions 42 30 [80] of by-products. The fuel thus gets deteriorated as there is
Under anaerobic conditions 18 50 [80] formation of sediment and gum. Peroxide formation
2366 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

through this route leads to obligomerization even at ambi- converted to glycerol. In each of the steps an ester is
ent temperature. As the deterioration of biodiesel is attrib- formed. Thus three esters are obtained from one triglycer-
uted to the formation of peroxide in the initial step, the ides molecule.
remedy suggested is to prevent peroxide formation during K1
the stages of biodiesel manufacture and throughout its dis- TG þ M $ DG þ FAME ð2Þ
K4
tribution chain [12,81]. As biodiesels are primarily made K2
from vegetable oils which do contain naturally occurring DG þ M $ MG þ FAME ð3Þ
K5
antioxidants such as tocopherols, sterols and tocotrienols K3
and these remain in the biodiesel during the process of MG þ M $ G þ FAME ð4Þ
K6
manufacture. However, the distillation and purification
step destroys these natural antioxidants and hence becomes where, TG, triglycerides; DG, diglycerides; MG, mono-
prone to oxidation. Synthetic antioxidants such as phenolic glycerides; M, methanol and FAME, fatty acid methyl
types or aminic types have to be added to make it stable esters.
and hence acceptable in market [12,81,83–85]. Sarin et al. The values of rate constants for forward reactions, K1,
[12] suggested blending jatropha biodiesel with palm bio- K2 and K3, are found to be 5.00, 4.93 and 29.67 dm3 mol1
diesel to reduce the antioxidant dosage by 80–90% to main- min1 and the values of the rate constants of backward
tain good oxidation stability. reactions involved in the kinetics of biodiesel development,
K4, K5, and K6 are reported to be 3.54, 2.99 and
0.79 dm3 mol1 min1. A software MATLAB 6.1 was used
7. Kinetics of the reaction to generate concentration profile of glycerol, tri-,di-, and
monoglycerides and fatty acid methyl ester. Fig. 6 shows
Transesterification reaction consists of a sequence of the concentration profiles of all components in which a pla-
reversible reactions [52]. teau is reached at equilibrium [52].

ð1Þ

In the first step, triglycerides are converted to diglycerides 8. Diesel engine emissions and performance of biodiesel
which get converted to monoglycerides in the next
step. In the third and last step, monoglycerides are Researchers worldwide are on a consensus that biodie-
sel, irrespective of the feedstock used results in a decrease
in the emissions of hydrocarbons (HC), carbon monoxide
(CO), particulate matter (PM) emissions and sulphur diox-
ide (SO2). Only oxides of nitrogen (NOx) are reported to
increase which is due to oxygen content in the biodiesel
[86–94]. It is also said to be carbon neutral as it contributes
no net carbon dioxide to the atmosphere [95–97]. However,
in a study conducted by Sahoo et al. [8] the NOx emission
from 100% biodiesel lowered to 4% for polanga seed oil.
This is attributed by the authors to difference in engine
geometry, compression ratio, less reaction time and tem-
perature. A remarkable decrease in the emission of unburnt
hydrocarbon was observed. 40% reduction of CO2 emis-
sions was observed for B20 and B100 biodiesel. Thermal
efficiency of the engine also improved by 0.1%. Smoke
emissions reduced by 35% in the case of B60 biodiesel.
The results were obtained without any engine hardware
modifications. Other authors have suggested various strat-
Fig. 6. Simulated concentration profile of glycerol (G), tri-glyceride (TG),
egies to eliminate the NOx emission. Szybist et al. [98] sug-
di-glyceride (DG), mono-glyceride (MG) and fatty acid methyl ester gested to change the chemical composition of feedstock by
(FAME) during transesterification. increasing the methyl oleate and addition of cetane improv-
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2367

Table 8 be safe above which it would cause maintenance problem


Emission impact of 20 vol% biodiesel for soybean based biodiesel added to and might damage the engine. A study on comparison of
an average base diesel fuel
carbonyls emissions from diesel and biodiesel blend was
Percent change in emissions carried by Correa and Arbilla [104]. Higher emission of
NOx (nitrogen oxides) +2.0 formaldehyde, acetaldehyde, acrolein, acetone, propional-
PM (particulate matter) 10.1 dehyde, and butyraldehyde was observed from B2, B5,
HC (hydrocarbons) 21.1
CO (carbon monoxides) 11.0
B10 and B20 blends than neat diesel. However, significant
reduction in emission in terms of benzaldehyde was
observed from biodiesel blends.
ers. This reduces the iodine value. Boehman et al. [99] and Srivastava and Verma [54] have reported the HC, CO
Kegl [100] recommended to retard the injection timing and NO emissions from karanja oil methyl ester to be
which could lead to decrease in NOx emission. Nabi slightly higher as compared with petrodiesel. HC emission
et al. [101] advocated for the exhaust gas recirculation to of diesel at maximum load was 85 ppm, while that of bio-
reduce the NOx emission. diesel was 120 ppm due to poor mixing with air. CO emis-
Kegl [102] stressed on the importance of fuel injection sion of diesel at maximum load was reported to be 0.18%
system to reduce the engine emissions as well as fuel con- as compared to 0.21% of biodiesel and NO emission was
sumption. Author suggests that pressure squareness (ratio reported to be 12% higher than that of biodiesel. Maximum
of mean to maximum injection pressure) should be at max- thermal efficiency of methyl ester and brake specific fuel
imum and fuelling in the first part of injection has to be less consumption of the biodiesel were quite close to that of die-
to reduce NOx emission. Simultaneously, the fuelling in the sel and hence the authors were of the view that karanja oil
last part of injection should be less to reduce the smoke methyl ester can replace diesel as an alternative fuel. Table
emissions. Shahid and Jamal [103] reported that blend of 8 depicts emission impact of 20 vol% for soybean based
biodiesel till B20 (20% biodiesel and 80% diesel) would biodiesel. It can be seen that there is a significant reduction

Table 9
List of 26 indigenous plant meeting US, Germany and European standards (a oil from kernel, b oil from seeds, osa: other saturated acids, uk: unknown) [107]
Sources Oil SN IV CN Fatty acid composition (%)
Rhus succedanea Linn 39.5a 204.0 92.6 52.22 16:0 (25.4); 18:1 (46.8); 18:2 (27.8)
Annona reticulate Linn 42.0b 203.6 87.2 53.47 14:0 (1.0); 16:0 (17.2); 16:1 (4.2); 18:0 (7.5); 18:1 (48.4); 18:2 (21.7)
Ervatamia coronaria 41.6b 201.1 76.0 56.33 16:0 (24.4); 16:1 (0.2); 18:0 (7.2); 18:1 (50.5); 18:2 (15.8); 18:3 (0.6); 20:0 (0.7); 20:1 (0.2); 22:0
Stapf (0.2); uk (0.2)
Thevetia peruviana 67.0a 201.5 84.0 57.48 16:0 (15.6); 18:0 (10.5); 8:1 (60.9); 18:2 (5.2); 18:3 (7.4); 20:0 (0.3); 22:0 (0.1)
Merrill
Basella rubra Linn 36.9b 202.9 85.3 54.00 14:0 (0.4); 16:0 (19.7); 16:1 (0.4); 18:0 (6.5); 18:1 (50.3); 18:2 (21.6); 18:3 (0.4); 20:4 (0.7)
Canarium commune Linn 73.0a 204.6 77.3 55.58 16:0 (29.0); 18:0 (9.7); 18:1 (38.3); 18:2 (21.8); 18:3 (1.2)
Celastrus paniculatus 52.0a 236.6 77.5 51.9 1:0 (2.0); 2:0 (1.7); 16:0 (25.1); 18:0 (6.7); 18:1 (46.1); 18:2 (15.4); 18:3 (3.0)
Linn
Terminalia bellirica Roxb 40.0b 198.8 77.8 56.24 16:0 (35.0); 18:1 (24.0); 18:2 (31.0); osa (10.0)
Vernonia cinerea Less 38.0a 205.2 68.5 57.51 14:0 (8.0); 16:0 (23.0); 18:0 (8.0); 18:1 (32.0); 18:2 (22.0); 20:0 (3.0); 22:0 (4.0)
Corylus avellana 57.5a 200.5 84.51 54.50 14:0 (3.2); 16:0 (3.1); 18:0 (2.6); 18:1 (88.0); 18:2 (2.9); uk (0.2)
Jatropa curcas Linn 40.0b 202.6 93.0 52.31 14:0 (1.4); 16:0 (15.6); 18:0 (9.7); 18:1 (40.8); 18:2 (32.1); 20:0 (0.4)
Putranjiva roxburghii 41.8a 199.6 82.9 54.99 16:0 (8.0); 18:0 (15.0); 18:1 (56.0); 18:2 (18.0); 20:0 (3.0)
Calophyllum apetalum 47.5a 200.4 97.6 51.57 16:0 (8.0); 18:0 (14.0); 18:1 (48.0); 18:2 (30.0)
Wild
Calophyllum inophyllum 65.0a 201.4 71.5 57.3 16:0 (17.9); 16:1 (2.5); 18:0 (18.5); 18:1 (42.7); 18:2 (13.7); 18:3 (2.1); 24:0 (2.6)
Linn
Mesua ferrea Linn 68.5a 201.0 81.3 55.10 14:0 (0.9); 16:0 (10.8); 18:0 (12.4); 18:1 (60.0); 18:2 (15.0); 20:0 (0.9)
Azadirachta indica 44.5a 201.1 69.3 57.83 16:0 (14.9); 18:0 (14.4); 18:1 (61.9); 18:2 (7.5); 20:0 (1.3)
Moringa concanensis 35.5b 199.7 76.0 56.32 16:0 (9.7); 18:0 (2.4); 18:1 (83.8); 18:2 (0.8); 20:0 (3.3)
Nimmo
Moringa oleifera Lam 35.0a 199.7 75.4 56.66 16:0 (9.1); 16:1 (2.1); 18:0 (2.7); 18:1 (79.4); 18:2 (0.7); 18:3 (0.2); 20:0 (5.8)
Pongamia pinnata Pierre 33.0b 196.7 80.9 55.84 16:0 (10.6); 18:0 (6.8); 18:1 (49.4); 18:2 (19.0); 20:0 (4.1); 20:1 (2.4); 22:0 (5.3); 24:0 (2.4)
Ziziphus mauritiana Lam 33.0b 198.6 81.8 55.37 16:0 (10.4); 18:0 (5.5); 18:1 (64.4); 18:2 (12.4); 20:0 (1.8); 20:1 (2.6); 22:0 (1.2); 22:1 (1.7)
Sapindus trifoliatus Linn 45.5a 195.0 64.5 59.77 16:0 (5.4); 18:0 (8.5); 18:1 (55.1); 18:2 (8.2); 20:0 (20.7); 22:0 (2.1)
Schleichera oleosa Oken 40.0b 193.0 57.9 61.55 16:0 (1.6); 16:1 (3.1); 18:0 (10.1); 18:1 (52.5); 20:0 (19.7); 22:0 (4.0); 22:1 (0.9); gadolic acid (8.4)
Madhuca indica JF Gmel 40.0b 202.1 74.2 56.61 14:0 (1.0); 16:0 (17.8); 18:0 (14.0); 18:1 (46.3); 18:2 (17.9); 20:0 (3.0)
Mimusops hexendra 47.0a 202.0 62.2 59.32 16:0 (19.0); 18:0 (14.0); 18:1 (63.0); 18:2 (3.0); 20:0 (1.0)
Robx
Pterygota alata Rbr 35.0b 202.6 98.4 51.09 16:0 (14.5); 18:0 (8.5); 18:1 (44.0); 18:2 (32.4); uk (1.0)
Holoptelia integrifolia 37.4b 208.7 49.9 61.22 14:0 (3.5); 16:0 (35.1); 16:1 (1.9); 18:0 (4.5); 18:1 (53.3); 20:0 (1.1); uk (1.4)
2368 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

Table 10
List of 11 species meeting the US biodiesel standards on the basis of fatty acid composition, SN, IV and CN (a oil from kernel, b oil from seeds, osa: other
saturated acids, uk: unknown) [107]
Sources Oil SN IV CN Fatty acid composition (%)
Vallaris solanacea 33.0b 198.3 104.7 50.26 16:0 (7.2); 18:0 (14.4); 18:1 (35.3); 18:2 (40.4); 20:0 (1.8); 22:0 (0.4); 24:0 (0.5)
Kuntze
Balanites roxburghii 43.0a 188.9 109.9 50.46 16:0 (17.0); 16:1 (4.3); 18:0 (7.8); 18:1 (32.4); 18:2 (31.3); 18:3 (7.2)
Planch
Croton tiglium Linn 45.0b 203.9 102.9 49.9 14:0 (11.0); 16:0 (1.2); 18:0 (0.5); 18:1 (56.0); 18:2 (29.0); 20:0 (2.3)
Hydnocarpus wightiana 63.0a 210.5 102.1 49.25 16:0 (1.8); 18:1 (6.9); hydnocarpic acid (48.7); gorlic acid (12.2); chaulmoogric acid (27.0);
Blume chaulmoogtic homolog (3.4)
Mappia foetida Milers 48.0b 200.7 101.3 50.70 16:0 (7.1); 18:0 (17.7); 18:1 (38.4); 18:3 (36.8)
Perilla frutescens 40.5b 199.0 193.9 30.09 18:1 (9.8); 18:2 (47.5); 18:3 (36.2); osa (6.5)
Britton
Aphanamixis 35.0a 203.8 109.1 48.52 16:0 (23.1); 18:0 (12.8); 18:1 (21.5); 18:2 (29.0); 18:3 (13.6)
polystachya Park
Princeptia utilis Royle 37.2a 201.9 108.4 48.94 14:0 (1.8); 16:0 (15.2); 18:0 (4.5); 18:1 (32.6); 18:2 (43.6); 24:0 (0.9) uk (1.4)
Meyna laxiflora Robyns 38.5b 202.8 101.3 50.42 16:0 (18.8); 18:0 (9.0); 18:1 (32.5); 18:2 (39.7)
Aegle marmelos correa 34.0b 202.5 114.9 48.30 16:0 (16.6); 18:0 (8.8); 18:1 (30.5); 18:2 (36.0); 18:3 (8.1)
Roxb
Tectona grandis Linn 44.5a 200.9 111.3 48.31 14:0 (0.2); 16:0 (11.0); 18:0 (10.2); 18:1 (29.5); 18:2 (46.4); 18:3 (0.4); 20:0 (2.3)

in HC (21%), CO (10%), PM (11%) and 2.0% increase in and 19.9 million ha, respectively, will meet the target of
NOx emission [105]. 100% replacement of imported biodiesel which amounted
to 87.5 million tons in 2003–2004. These 37 species are
9. Indian scenario listed in Tables 9 and 10. Among these species, jatropha
(Jatropha curcas), karanja (P. pinnata), neem (A. indica),
India imports more than 40% of its edible oil require- mahua (Madhuca indica) and polanga (Calophyllum
ment and hence non-edible oils are used for the develop- inophyllum) have catched the attention of researchers and
ment of biodiesel. India is a agrarian nation and has rich biodiesel manufacturer in India and feasibility of rest of
plant biodiversity which can support the development of the plant species still remains unexplored.
biodiesel. India also has a vast geographical area with agri-
cultural lands as well as wastelands on which oil bearing 10. Cost of biodiesel
plants can be planted. Common non-edible oil bearing
plants and trees include neem, karanja, mahua, jatropha, Various factors contributing to the cost of biodiesel
etc. The oil yields from these species at present are insuffi- include raw material, other reactants, nature of purifica-
cient to meet the demand for raw material on large scale tion, its storage, etc. However, the major factor which con-
production of biodiesel. Hence, there has been government tributes the cost of biodiesel production is the feedstock,
initiatives and interest from few private firms to enhance which is about 80% of the total operating cost [108]. Cost
the production and distribution facilities of biodiesel of biodiesel reported by Zhang et al. [29] is US $0.5 l1
throughout the country. The Petroleum Ministry has set as compared to US $0.35 for normal diesel. Bender in his
a target for biodiesel to meet 20% of India’s diesel demand. review has reported the cost of biodiesel to be US
Government’s initiative has resulted in large scale planta- $0.30 l1 and US $0.69 l1 when the fuel was produced
tion of J. curcas in the state Andhra Pradesh. Oil and Nat- from soybean and rapeseed respectively. The intact oilseed
ural Gas Corporation (ONGC) has planned to build an was taken as starting material while calculating the cost.
export oriented refinery at kakinada in Andhra Pradesh Canakci and Van Gerpen while using a small pilot scale
which will have a annual production capacity of 5.5–7.5 plant in a batch process estimated the cost to be US
million tonnes [106]. $0.42 l1 while using refined, bleached and deodorized soy-
Azam et al. [107] have studied the profile of 75 indige- bean oil. The profits from glycerol and capital cost for
nous plant species of India containing 30% or more oil in operation was not included [109,110].
their seed, fruit or nut. Out of these plants, based on sapon- Haas et al. [111] in a study of review on biodiesel pro-
ification number, iodine value, cetane number and fatty duction cost found the feedstock to contribute a substantial
acid composition, 26 species were found to be most suitable portion in production cost. A process model was prepared
for use as biodiesel and they met the biodiesel standards of by the author to estimate biodiesel production costs. Tak-
USA (ASTM D 6751-02, ASTM PS 121-99), Germany ing all the factors into account viz. raw material (vegetable
(DIN V 51606) and European Standard Organization oil, methanol, catalysts), utilities (electricity, etc.), labour,
(EN 14214). Another 11 plant species met the specifications supplies, general works and depreciation, the cost of bio-
of US biodiesel standards. Authors predicts that cultiva- diesel was estimated to be US $0.561 l1. The coproduct
tion of Azardirachta indica or P. pinnata on 40.09 million glycerol as 80% w/w aqueous solution was valued to be
Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373 2369

US $0.034 l1 and reduced the production cost of biodiesel Biodiesel comprises of 11% oxygen by weight which
by 6% on deduction of this value from original cost. Hence, improve the combustion process and hence has reduced
the gross operating cost of biodiesel was estimated to be emissions in terms of hydrocarbon, carbon monoxide and
US $0.527 l1, of which the feedstock comprised 87.36% particulate emissions but increases nitrogen oxide emis-
of the overall cost of biodiesel production. sions. Nitrogen oxide emissions from biodiesel can be
Nas and Berktay [112] too concluded that feedstock cost reduced by adding cetane enhancers that are di-tert-butyl
is the major component contributing to the cost of biodie- peroxide at 1% or 2-ethylhexyl nitrate at 0.5%. However,
sel production. In a comparison of feedstock viz. soybean addition of these enhancers will increase the cost of biodiesel
oil and yellow grease (recycled cooking oil from restau- production. Nevertheless, reduction in emission of oxides of
rants), it was estimated that yellow grease is quite less nitrogen is desired as they are ozone precursors and after
expensive that soybean oil. On the contrary, the supply reaching stratosphere it will result in ozone layer depletion.
of yellow grease is limited and has other applications and In Indian context, the government has fixed the price of
hence it cannot be used on a large scale production. An biodiesel delivered at refineries to be Rs. 26.50 l1. This
eight year comprehensive study (from 2004–2005 to rate of biodiesel has been fixed after the Indian government
2012–2013), on the price rise of petroleum diesel, yellow has provided subsidies in order to encourage its application
grease and soybean oil is reported. Cost of petroleum has [113].
been estimated to rise from 0.67 to 0.75 (i.e. 11.94% The cost of biodiesel after blending with petrodiesel will
increase). Biodiesel fuel obtained from yellow grease is esti- reduce as the cost of biodiesel becomes less significant in
mated to rise from 1.41 to 1.55 (i.e. 9.93% increase). Biodie- blended form. At present, biodiesel can be blended with
sel fuel from soybean oil will rise from 2.54 to 2.80 (i.e. 80% petrodiesel (B20) without any engine modification. B
10.24% increase). Author is of opinion that biodiesel will 100 (100% biodiesel) costed US $3.76 per gallon of biodie-
not be produced at a cost comparable with that of petro- sel in USA in June 2006, whereas, B 20 (20% biodiesel and
diesel unless the soybean oil price decline. 80% petrodiesel) costed US $2.98 per gallon of biodiesel.

Table 11
Instrumentation involved in characterization of biodiesel
Feedstock Instrument involved for characterization Reference
Tobacco High performance liquid chromatograph [7]
Polanga seed oil High performance liquid chromatograph [8]
Pongamia pinnata (i) HPLC (Perkin-Elmer series 200) equipped with refractive index detector (shodex RI 71) [11]
(ii) H NMR Bruker DPX 300 spectrometer (Bruker, Rheinstetten, Germany)
(iii) Gas chromatograph (for analysis of fatty acid composition of karanja oil)
Jatropha, Pongamia, sunflower, (i) GC (Model HR/GC/5300) [for fatty acid composition of vegetable oils) [12]
soybean, palm (ii) Thin layer chromatography (TLC)
Pongamia pinnata Gas chromatography (Nucon, India) equipped with a FID detector [14]
Waste cooking oil Gas chromatography (GC) equipped with a capillary column (SPBTM-5, 30 m  0.32 mm  0.25 [16]
lm) and a FID
Neat and used frying oil (i) HP 6890 series II Gas Chromatograph with a 3365/II GC-chemstation and a FID [19]
(ii) Thin layer chromatography (TLC)
Sunflower oil (i) Gel permeation chromatograph (GPC) [20]
(ii) Gas chromatograph (GC), Nucon 5765, India
Microalgal oil CE-440 elemental analyzer (for determining elemental composition of biodiesel) [21]
Microalga chlorella protothecoides Gas Chromatography–mass spectrometric analysis [22]
Soybean oil (i) X-ray diffractometer [23]
(ii) GPC with an RI (refractive index) detector, (carrier: THF)
(iii) Gas chromatography–mass spectrometer
Lipid extracted from the cell of R. Gas chromatograph [24]
glutinis
Triolein HPLC system (Hitachi, Ltd, Tokyo, Japan, D-7000 interface, L-7100 [26]
Sunflower oil For FAME determination Agilent 6890 GC with a HP INNOwax capillary column [27]
For catalyst characterization
(i) Balzer Prisma quadrupole mass spectrometer (QMS 200)
(ii) Seifert 3000 XRD diffractometer (equipped with a PW gonimeter)
(iii) VG Escalab 200 R spectrometer (equipped with a hemispherical electron analyzer)
(iv) Nicolet 5700 Fourier transform spectrophotometer (equipped with an Hg-col-Te
cryodetector)
Biopiles Gas chromatography–mass spectrometer [79]
Canola, corn, peanut, olive, waste Gas chromatography [85]
vegetable
Castor oil (i) Size exclusion chromatography (SEC) [104]
(ii) Fourier-transformed infrared spectroscopy
2370 Y.C. Sharma et al. / Fuel 87 (2008) 2355–2373

11. Instrumentation involved in biodiesel production excess molar ratio has been used for biodiesel production
for better yield in lesser time. The molar ratio employed
For production of biodiesel, there are some primary during acid esterification is between 6:1 and 18:1 whereas
steps. If kernel or seeds are taken as starting materials, in the molar ratio used alkaline transesterification ranges
first step the raw oil is to be expelled from the kernel by between 5:1 and 12:1 after reducing the acid value to less
mechanical crusher. This raw oil is in fact feedstock for than 2.0% approximately. The temperature ranges between
development of biodiesel. After feedstock is obtained, 318 and 338 K as the boiling point of methanol is 337.7 K
beakers, measuring flasks, test tubes, separating funnels, and heating beyond this temperature would burn metha-
etc. are needed up to development of biodiesel. Practically nol. However, higher temperature is employed while using
no instruments are needed till its development. Most of the supercritical methanol (473–573 K). Depending on the
instruments are used for characterization of the biodiesel feedstock taken; amount and type of alcohol and catalyst;
product. Further, the instruments used for characterization temperature employed; mode and rate of stirring; there is
can be divided into the categories of minor and major difference in the yield of biodiesel which varied from 80
equipments. Viscometer, cetane number analyzer, etc. are to 100%. The percent conversion of biodiesel also ranged
minor equipments. Flash point, cloud point, pour point, between 80% and 100%.
etc. are also determined by minor instruments. Major Another added advantage of biodiesel is that it is biode-
instruments are however, needed for chemical characteriza- gradable in nature. When used as blend along with diesel
tion of biodiesel product. Gas chromatograph, gas chro- fuel, it shows positive synergic effect of biodegradation by
matograph–mass spectrometer, high performance liquid means of cometabolism. Major disadvantage of biodiesel
chromatograph, fourier transformed infrared spectrome- is the inverse relationship of oxidation stability of biodiesel
ter, elemental analyzer etc. are the major instruments used with its low temperature properties which includes cloud
for chemical characterization of the product. The major point and pour point. Higher composition of saturated fatty
instruments are listed in Table 11. acids in feedstock will increase the oxidation stability of bio-
diesel but will lower its cloud and pour points. Whereas,
12. Conclusions higher composition of unsaturated fatty acids will enhance
the cloud point and pour point of biodiesel but will have a
Biodiesel is derived from a varied range of vegetable oil poor oxidation stability. Hence, a balance has to be main-
(edible and non-edible), animal fats, used frying oil, waste tained between the ratio of saturates and unsaturates for
cooking oil and wastewater. The edible oil in use at present the oil to be used as a feedstock for biodiesel production.
is soybean, sunflower, canola, palm. The non-edible oil used Edible oils are in use in developed nations such as USA
as feedstock for biodiesel production includes J. curcas, P. and European nations but developing nations are not self
pinnata, M. indica, F. elastica, A. indica, C. inophyllum, sufficient in the production of edible oils and hence have
etc. The main advantage in its usage is attributed to lesser emphasized in the application of a number of non-edible
exhaust emissions in terms of carbon monoxide, hydrocar- oils. In a country like India, which is rich in plant biodiver-
bons, particulate matter, polycyclic aromatic hydrocarbon sity, there are many plant species whose seeds remain
compounds and nitrited polycyclic aromatic hydrocarbon unutilized and underutilized have been tried for biodiesel
compounds. Biodiesel is said to be carbon neutral as more production. These species have shown promises and fulfills
of carbon dioxide is absorbed by the biodiesel yielding various biodiesel standards. However, there still is paucity
plants than what is added to the atmosphere when used as in terms of all the standards which should be fulfilled for
fuel. Exhaust emissions of NOx can be controlled by adopt- the large commercial application and its acceptance from
ing certain strategies such as change in composition of feed- public and governing bodies.
stock, addition of cetane improvers, retardation of injection
timing, exhaust gas recirculation, etc.
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