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Advancements in Development and Characterization of Biodiesel a Review

Advancements in Development and Characterization of Biodiesel a Review

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Published by: Samran Ali on Oct 02, 2010
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Review article
Advancements in development and characterizationof 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 2008Available 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 byday. 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23561.1. Various raw materials used as feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23572. Production of biodiesel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23602.1. Acid esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23602.2. Alkaline transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23603. A special reference to karanja . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23624. Effect of different parameters on production of biodiesel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23634.1. Effect of molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23634.2. Effect of moisture and water content on the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23634.3. Effect of free fatty acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23644.4. Effect of temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23644.5. Effect of stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23644.6. Effect of specific gravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23655. Biodegradability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23656. Stability of biodiesel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23657. Kinetics of the reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23668. Diesel engine emissions and performance of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366
0016-2361/$ - see front matter
Ó
2008 Elsevier Ltd. All rights reserved.doi:10.1016/j.fuel.2008.01.014
*
Corresponding author. Tel.: +91 542 2307025 (O), +91 9935616119 (M); fax: +91 542 2316428.
E-mail address:
www.fuelfirst.com
 Available online at www.sciencedirect.com
Fuel 87 (2008) 2355–2373
 
9. Indian scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236810. Cost of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236811. Instrumentation involved in biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237012. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
1. Introduction
Whenever I think of fuel, a picture of villages of devel-oping nations eclipsed in darkness, full of poverty, noplanned mechanization, agriculture depending on rainGod for irrigation comes before my eyes. Be it lightingthe house, agriculture, or cooking, each process requiresenergy. Energy, most countries do not have energy evento light the cities! Superconductivity and hydrogen energyreflected some promise but these were completely short-lived. Biodiesel, yes, probably biodiesel is the FUEL of future.Biodiesel is derived from vegetable oils and hence is arenewable fuel. Gasoline and diesel come in the categoryof non-renewable fuel and will last for a limited period of time. These non-renewable fuels also emit pollutants inthe form of oxides of nitrogen, oxides of sulphur, carbondioxide, carbon monoxide, lead, hydrocarbons, etc. duringtheir processing and use. A renewable fuel such as biodie-sel, with lesser exhaust emissions, is the need of the day.Hence, researchers and scientific community worldwidehave focused on development of biodiesel and the optimi-zation of the processes to meet the standards and specifica-tions needed for the fuel to be used commercially withoutcompromising on the durability of engine parts. The inter-est in the use of renewable fuel started with the direct use of vegetable oils as a substitute for diesel. However, theirdirect use in compression ignition engines was restricteddue to high viscosity which resulted in poor fuel atomiza-tion, incomplete combustion and carbon deposition onthe injector and the valve seats causing serious engine foul-ing[1]. Other constraints of the direct application of vege-table oil were its low volatility and polyunsaturatedcharacter. To overcome these constraints, the processes likepyrolysis, micro-emulsification, transesterification, etc.were especially developed. Pyrolysis of the vegetable oilresulted in products with low viscosity, high cetane num-ber, accepted amounts of sulphur, water and sediments,accepted copper corrosion values but were unacceptablein the terms of their ash contents, carbon residues, andpour points. Similarly, micro-emulsion of vegetable oillowered the viscosity of the oil but resulted in irregularinjector needle sticking, heavy carbon deposits and incom-plete combustion during 200 h laboratory screening endur-ance test[2]. Transesterification is a chemical reactionbetween triglyceride and alcohol in the presence of a cata-lyst. It consists of a sequence of three consecutive reversiblereactions where triglycerides are converted to diglycerides,diglycerides are converted to monoglycerides followed bythe conversion of monoglycerides to glycerol. In each stepan ester is produced and thus three ester molecules are pro-duced from one molecule of triglyceride[3]. Out of thesethree methods, transesterification is the most viable processadopted known so far for the lowering of viscosity. It alsogives glycerol as a by-product which has a commercialvalue.Stoichiometrically, three moles of alcohol are requiredfor each mole of triglyceride, but in general, a higher molarratio is often employed for maximum ester productiondepending upon the type of feedstock, amount of catalyst,temperature, etc. Commonly used alcohols include metha-nol, ethanol, propanol and butanol. However, the yield of biodiesel is independent of the type of the alcohol used andthe selection of one of these depends on cost and perfor-mance. Methanol is preferred over others due to its lowcost[1]. The conventional catalysts used are acid and alkalicatalysts depending upon the nature of the oil used for bio-diesel production. Another catalyst being studied is lipase.Lipase has advantage over acid and alkali catalysts but itscost is a limiting factor for its use in large scale productionof biodiesel. Choice of acid and alkali catalysts depends onthe free fatty acids (FFA) content in the raw oil. FFAshould not exceed a certain amount for transesterificationto occur by an alkali catalyst. Invariably, on all aspectsof development of biodiesel, Ma and Hanna[4]have donesignificant work. Canakci and Van Gerpan[5,6]reportedthat transesterification was not feasible if FFA content inthe oil was about 3%. Ramadhas et al.[1]and Veljkovicet al.[7]used rubber seed oil and tobacco seed oil, respec-tively, with higher free fatty acid content (17%). Theauthors reduced the FFA value to more than 2.0%, whichcorresponds to 4.0 mg KOH/g, by acid esterification usingH
2
SO
4
as a catalyst. Sahoo et al.[8]used zero catalyzedtransesterification (using toluene) and acid esterification(using H
2
SO
4
) prior to alkaline esterification to reducethe acid value from 22.0% to 2.0%. Sharma and Singh[3]also favored acid esterification prior to alkaline transesteri-fication with karanja oil as feedstock having FFA of 2.53%(5.06 mg KOH/g) using H
2
SO
4
. In the same manner, theacid value of jatropha which corresponds to 14% FFAwas reduced to less than 1% by using H
2
SO
4
[9].Table 1depicts the values of initial FFA of the feedstock, the levelreached after acid esterification and the amount of H
2
SO
4
used. After treatment with acid catalyst, H
2
SO
4
, the freefatty acid (FFA) value is reduced to less than 2.0% to maketransesterification reaction feasible.Table 2depicts theyield/conversion of biodiesel with different oils taken.The yield of biodiesel ranged from 56% from
Chlorella
2356
Y.C. Sharma et al./Fuel 87 (2008) 2355–2373
 
 protothecoides
to 99% from
Jatropha curcas
. The conver-sion of biodiesel ranged from more than 80% from
C. prothecoides
to 98.4% from soybean oil.Various oils have been in use in different countries asraw materials for biodiesel production owing to its avail-ability. Soybean oil is commonly used in United Statesand rapeseed oil is used in many European countries forbiodiesel production, whereas, coconut oil and palm oilsare used in Malaysia for biodiesel production[10–13].Transesterification of edible oils has also been carried outfrom the oil of canola and sunflower. Other edible andnon-edible oils, animal fats, algae and waste cooking oilshave also been investigated by researchers for the develop-ment of biodiesel[14–31].Table 3depicts the work carried out for biodiesel production from various feedstocks underdifferent conditions. Type and amount of variables such asfeedstock, alcohol, molar ratio, catalyst, reaction tempera-ture, time duration, rate and mode of stirring affects theyield and conversion of biodiesel.
1.1. Various raw materials used as feedstock 
Leung and Guo[19]compared the transesterificationreaction conditions of neat canola oil with used frying oil(UFO). A comparatively higher temperature (333 K),higher molar ratio (7:1, methanol/UFO), and more amountof catalyst (1.1 wt% NaOH) was needed when compared toedible canola oil where optimal conditions were 315– 318 K, 6:1 methanol/oil molar ratio and 1.0 wt% NaOH.However, comparatively a less time (20 min) was neededin UFO for completion of reaction in comparison to canolaoil where reaction time took 60 min. Non-edible oils usedfor transesterification mostly are the oils with higher freefatty acids such as rubber (
Ficus elastica
), jatropha (
J. cur-cas
), karanja (
Pongamia pinnata
), mahua (
Madhuca indica
),polanga (
Calophyllum inophyllum
), tobacco (
Nicotina taba-cum
), etc. In an attempt to reduce the cost of biodiesel, mic-roalgal oils have also been tried by researchers as a sourceof feedstock for the production of biodiesel due to theirhigher photosynthetic efficiency, higher biomass produc-tion and faster growth as compared to other energy crops[32–35]. Miao and Wu[21]reported production of biodie- sel from microalga
C. protothecoides
using 100% catalystquantity (based on oil weight) with 56:1 molar ratio of methanol to oil at temperature of 303 K in 4 h of reactiontime. The specific gravity of biodiesel produced reducedfrom initial value of 0.91 to a final value of 0.86. Xuet al.[22]obtained high quality and low cost biodiesel frommicroalgae
C. protothecoides
of heating value 41 MJ kg
À
1
,density 0.864 kg L
À
1
and viscosity 5.2
Â
10
À
4
Pa S at313 K.
C. protothecoides
have earlier been reported as afeedstock for aquaculture feeds, human food supplementsand pharmaceuticals[36–39].Attributing to its low cost, waste cooking oil has alsobeen tried by researchers to develop biodiesel. The ideacomes from the fact that triglycerides comprise of greasesand oil. Oils are generally in liquid state at room tempera-ture, whereas greases and fats are in solid state at roomtemperature. Recycled grease is termed as waste greaseand is classified as yellow and brown grease dependingon free fatty acid composition[17]. The price of yellowgrease (FFA < 15%) ranges from $0.04 to $0.09 kg
À
1
whilethe price of brown grease (FFA > 15%) ranges between0.004 and $0.014 kg
À
1
[40]. Biodiesel development fromgrease can reduce its production cost. In United States,an estimate reveals that biodiesel production from 5.2 bil-lion kg/year of greases and animal fats could replace 1.5million gallons of diesel fuel. The major constraint of directapplication of waste frying oil lies in its higher amount of 
Table 2Yield of biodiesel with different feedstockOil taken for study Yield(%)Conversion(%)ReferenceKaranja (
Pongamia pinnata
) 89.5 – [3]Tobacco (
Nicotina tabacum
) 91 – [7]Polanga (
Calophyllum inophyllum
) 85[8]Jatropha (
Jatropha curcas
) 99 – [9]Mahua (
Madhuca indica
) 98 – [10]Karanja (
Pongamia pinnata
) 9798 – [11]Karanja (
Pongamia pinnata
) 92/95[14]Soybean (
Glycine max
) 98.4[15]Waste cooking oil 97.02 – [16]Canola oil (
Brassica napus
) 90.04 98[19]Used frying oil 87.5 94[19]Sunflower oil (
Helianthus annuus
) – Nearlycomplete[20]
Chlorella protothecoides
56 – [21]
Chlorella protothecoides
>80[22]Table 1Values of initial FFA content of different feedstockFeedstock Initial FFA (%) FFA after treatment (%) Amount (%) and catalyst used ReferenceRubber oil 17.0 <2.0 0.5, H
2
SO
4
[1]Karanja oil 2.53 0.95 0.5, H
2
SO
4
[3]Tobacco oil 35.0 <2.0 1.0/2.0, H
2
SO
4
[7]Polanga oil 22.0 <2.0 0.65, H
2
SO
4
[8]Jatropha oil 14.0 <1.0 1.43, H
2
SO
4
[9]Mahua oil 19.0 <1.0 1.0, H
2
SO
4
[10]Karanja oil 2.53 0.3 KOH (appropriate amount)[11] 37.96 ± 0.018 1.05 ± 0.018 2.0 Fe
2
SO
4
[16] 40.0 <1.0 – [18]
Y.C. Sharma et al./Fuel 87 (2008) 2355–2373
2357

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