Journal of Dispersion Science and Technology

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Biofuels–Renewable Energy Sources: A Review

Iva Kralova & Johan Sjöblom

To cite this article: Iva Kralova & Johan Sjöblom (2010) Biofuels–Renewable Energy
Sources: A Review, Journal of Dispersion Science and Technology, 31:3, 409-425, DOI:
10.1080/01932690903119674

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Journal of Dispersion Science and Technology, 31:409–425, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903119674

Biofuels–Renewable Energy Sources: A Review

Iva Kralova and Johan Sjöblom
Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and
Technology (NTNU), Trondheim, Norway

Biodiesel is biodegradable and nontoxic, and it significantly reduces toxic and other emissions
when burned as a fuel. The advantages of biodiesel as diesel fuel are its portability, ready avail-
ability, renewability, higher combustion efficiency, non-toxicity, higher flash point, and lower
sulfur and aromatic content, higher cetane number, and higher biodegradability. The major
disadvantages of biodiesel are its higher viscosity, lower energy content, higher cloud point and
pour point, higher nitrogen oxide (NOx) emissions, lower engine speed and power, injector cok-
ing, engine compatibility, high price, and greater engine wear. The technical disadvantages of
biodiesel/fossil diesel blends include problems with fuel freezing in cold weather, reduced energy
density, and degradation of fuel under storage for prolonged periods. The sources of biodiesel are
vegetable oils and fats. The direct use of vegetable oils and/or oil blends is generally considered to
be unsatisfactory and impractical for both direct injection and indirect type diesel engines because
of their high viscosities and low volatilities injector coking and trumpet formation on the injectors,
higher level of carbon deposits, oil ring sticking, and thickening and gelling of the engine lubricant
oil, acid composition. Biodiesel is obtained by transesterifying triglycerides with methanol. A
popular variation of the batch transesterification process which needs high alcohol/acid ratio
(several separation problems and high corrosivity and toxicity) is the use of continuous stirred
tank reactors in series. This continuous process is heterogeneous and is based on reactive distil-
lation. The key factor is the selection of the right and effective solid catalyst which leads to
reduction of energy consumption and investments at all.
Keywords Biodiesel, biofuels, combustion, diesel engine, emissions, fatty acid methyl ester
(FAME), greenhouse gas emissions, heavy vehicles, process design, reaction
distillation, renewable energy sources (RES), transesterification, triglycerides,
vegetable oil

INTRODUCTION carbon dioxide produced, as well as reducing the levels

Renewable energy sources (RESs) are also often called of the pollutants. Table 1 shows the global renewable
alternative energy sources. The share of RESs is expected energy scenario by 2040. Approximately half of the global
to increase very significantly (30–80% in 2100). Biomass, energy supply will come from renewables in 2040, accord-
wind, and geothermal energy are commercially competitive ing to the European Renewable Energy Council in 2006.
and are making relatively fast progress.[1] Biomass now In developed countries there is a growing trend toward
represents only 3% of primary energy consumption in employing modern technologies and efficient bioenergy
industrialized countries. About 98% of carbon emissions conversion using a range of biofuels, which are becoming
result from fossil fuel combustion. Reducing the use of cost competitive with fossil fuels.[2]
fossil fuels would considerably reduce the amount of There are two global biomass-based liquid transpor-
tation fuels that might replace gasoline and diesel fuel.
These are bioethanol and biodiesel. It is generally held that
Received 12 May 2008; accepted 9 June 2009. biofuels offer many benefits, including sustainability,
The authors want to acknowledge fruitful discussions with reduction of greenhouse gas emissions, and security of
Drs. Jens-Emil Vindstad, Heidi Mediaas, and Knut Grande at supply.[3] A variety of fuels can be produced from biomass
Statoils R&D Center in Trondheim. StatoilHydro is acknowl-
resources including liquid fuels, such as ethanol, methanol,
edged for financial support and for the kind permission to publish
biodiesel, and Fischer-Tropsch diesel, and gaseous fuels,
the manuscript. The authors also acknowledge the comments by
Professor Ayhan Demirbas. such as hydrogen and methane. The biggest difference
Address correspondence to Iva Kralova, Ugelstad Laboratory, between biofuels and petroleum feedstocks is oxygen
Department of Chemical Engineering, Norwegian University of content. Biofuels have oxygen levels of 10–45% while
Science and Technology (NTNU), N-7491 Trondheim, Norway. petroleum has essentially none, making the chemical
E-mail: [email protected] properties of biofuels very different from those of

409
410 I. KRALOVA AND J. SJÖBLOM

TABLE 1 point and pour point, higher nitrogen oxide (NOx)

Global renewable energy scenario by 2040 emissions, lower engine speed and power, injector coking,
engine compatibility, high price, and greater engine wear.
2001 2010 2020 2030 2040 The technical disadvantages of biodiesel=fossil diesel
Total 10,038 10,549 11,425 12,352 13,310 blends include problems with fuel freezing in cold weather,
consumption reduced energy density, and degradation of fuel under
(million ton storage for prolonged periods.
oil equivalent) The competitiveness of biodiesel relies on the prices of
Biomass 1,080 1,313 1,791 2,483 3,271 biomass feedstock and costs, which are linked to conver-
Large hydro 22.7 266 309 341 358 sion technology. Depending on the feedstock used, bypro-
Geothermal 43.2 86 186 333 493 ducts may have more or less relative importance. Biodiesel
Small hydro 9.5 19 49 106 189 is not competitive with fossil diesel under current economic
Wind 4.7 44 266 542 688 conditions, where the positive externalities, such as impacts
Solar thermal 4.1 15 66 244 480 on the environment, employment, climate changes, and
Photovoltaic 0.2 2 24 221 784 trade balance, are not reflected in the price mechanism.
Solar thermal 0.1 0.4 3 16 68 The economic benefits of a biodiesel industry would
electricity include value added to the feedstock, an increased number
Marine (tidal= 0.05 0.1 0.4 3 20 of rural manufacturing jobs, increased income taxes,
wave=ocean) increased investments in plant and equipment, an
Total RES 1,365.5 1,745.5 2,694.4 4,289 6,351 expanded manufacturing sector, an increased tax base from
Renewable 13.6 16.6 23.6 34.7 47.7 plant operations and income taxes, improvement in the
energy source current account balance, and reductions in health care
contribution costs due to improved air quality and greenhouse gas
(%) mitigation. The production and utilization of biodiesel is
facilitated firstly through the agricultural policy of subsi-
dizing the cultivation of nonfood crops. Secondly, biodiesel
petroleum. In this study we focus on biodiesel, because it is exempt from the oil tax. The European Union accounted
burns like petroleum diesel and on the other hand biodiesel for nearly 89% of all biodiesel production worldwide in
probably has better efficiency than gasoline. Biodiesel also 2005. By 2010, the United States is expected to become
exhibits great potential for compression-ignition engines. the world’s largest single biodiesel market, accounting for
Diesel fuel can also be replaced by biodiesel made from roughly 18% of world biodiesel consumption, followed by
vegetable oils. Biodiesel is now mainly being produced Germany. The economic advantages of biodiesel are that
from soybean, rapeseed, and palm oils, is simple to use, it reduces greenhouse gas emissions, helps to reduce a
biodegradable, nontoxic, and basically free of sulphur country’s reliance on crude oil imports, and supports agri-
compounds and aromatics. Biodiesel is defined as the culture by providing new labor and market opportunities
mono-alkyl esters of fatty acids derived from vegetable oils for domestic crops. The cost of biodiesel fuels varies
or animal fats. depending on the base stock, geographic area, variability in
crop production from season to season, the price of crude
WHY TO CHOOSE BIODIESEL? petroleum, and other factors. The high price of biodiesel
Biodiesel is nonflammable and, in contrast to is in large part due to the high price of the feedstock.
petrodiesel, is nonexplosive, with a flash point of 423 K However, biodiesel can be made from other feedstocks,
for biodiesel as compared to 337 K for petrodiesel. Unlike including beef tallow, pork lard, and yellow grease. There-
petrodiesel, biodiesel is biodegradable and nontoxic, and fore, biodiesel is not competitive with petrodiesel under
it significantly reduces toxic and other emissions when current economic conditions. The competitiveness of
burned as a fuel. The advantages of biodiesel as diesel fuel biodiesel relies on the price of the biomass feedstock and
are its portability, ready availability, renewability, higher costs associated with the conversion technology.
combustion efficiency, and lower sulfur and aromatic
content,[4,5] higher cetane number, and higher biodegrad-
ability.[6–8] The main advantages of biodiesel given in the BIODIESEL SOURCES AND COMPOSITION
literature include its domestic origin, which would help Vegetable oils are renewable fuels. They have become
reduce a country’s dependency on imported petroleum, more attractive recently because of their environmental
its biodegradability, high flash point, and inherent lubricity benefits and the fact that they are made from renewable
in the neat form.[9,10] The major disadvantages of biodiesel resources. Vegetable oils are a renewable and potentially
are its higher viscosity, lower energy content, higher cloud inexhaustible source of energy, with energy content close
BIOFUELS 411

to that of diesel fuel. Global vegetable oil production listed in Table 2. As can be seen, palmitic (16:0) and stearic
increased from 56 million tons in 1990 to 88 million tons (18:0) are the two most common saturated fatty acids, with
in 2000, following a below-normal increase. The source every vegetable oil containing at least a small amount of
of this gain was distributed among the various oils. Global each one. Similarly, oleic (18:1) and linoleic (18:2) were
consumption rose 56 million tons to 86 million tons, the most common unsaturated fatty acids. Many of the oils
leaving world stocks comparatively tight. also contained some linolenic acid (18:3).
A variety of biolipids can be used to produce biodiesel: Tallow is a mixture of triglycerides, most of which are
saturated; tristearin is usually the major component.[4]
. virgin vegetable oil feedstock; rapeseed and
The tallow from animal sources is commonly used in soap
soybean oils are most commonly used, though
production. In tallow the saturated fatty acid component
other crops such as mustard, palm oil, sunflower,
accounts for almost 50% of the total fatty acids. The higher
hemp, and even algae show promise;
palmitic and stearic acid contents give tallow its unique
. waste vegetable oil;
properties of high melting point and high viscosity. Crude
. animal fats including tallow, lard, and yellow
tallow (beef) samples were used in pyrolysis and steam-
grease;
reforming procedures. The average composition of fatty
. nonedible oils such as jatropha, neem oil, castor
acids in tallow is in table. The total fatty acids in the tallow
oil, tall oil, etc.
samples were 51.1% by weight. The major fatty acids in the
In Malaysia and Indonesia, palm oil is used as a significant tallow were palmitic (28.7%), stearic (19.5), and oleic
biodiesel source. In Europe, rapeseed is the most common (44.4%). Higher palmitic and stearic acid contents give
base oil used in biodiesel production. In India and the tallow a high melting point.
Southeast Asia, the jatropha tree is used as a significant Tall oil, also called liquid rosin or tallol, is a viscous
fuel source. Tall oil, also called liquid rosin or tallol, is a yellow-black odorous liquid obtained as a byproduct of
viscous yellow-black odorous liquid obtained as a by- the Kraft process of wood pulp manufacture. Crude tall
product of the Kraft process of wood pulp manufacture oil contains rosins, unsaponifiable sterols (5–10%), resin
and seems to be good alternative of vegetable oils. The acids (mainly abietic acid and its isomers), fatty acids
major importers of vegetable oils are China, Pakistan, (mainly palmitic acid, oleic acid and linoleic acid), fatty
Italy, and the United Kingdom. A few countries such as alcohols, some sterols, and other alkyl hydrocarbon deri-
the Netherlands, Germany, the United States, and vates.[17] By fractional distillation tall oil rosin is obtained,
Singapore are both major exporters as well as importers with rosin content reduced to 10–35%. By further reduction
of vegetable oils.[11] of the rosin content to 1–10%, tall oil fatty acid (TOFA)
Vegetable oils are recovered from plants by chemical can be obtained, which is cheap, consists mostly of oleic
extraction using solvent extracts. The most common acid, and is a source of volatile fatty acids (Figure 1).
extraction solvent is petroleum-derived hexane. Another The rosin finds use as a component of adhesives, rubbers,
method of vegetable oil recovery is physical extraction,
which does not use solvent extracts. Supercritical carbon
dioxide can also be used for extraction and is TABLE 2
nontoxic.[12,13] Supercritical carbon dioxide effectively Fatty acid composition of vegetable oils and fats: xx:y
extracts vegetable oils and fats.[14] Supercritical fluid (xx–number of C atoms, y–number of double bonds,
extraction (SFE) can reduce sample preparation time, ABI–abietic acid, DeABI–dehydroabietic acid,
and recovery using the methods can be equal to or better Diol–(C20H42O2)
than that of the classical extraction techniques for solid Oil (refined) 16:0 16:1 18:0 18:1 18:2 18:3
and semisolid samples.[15] SFE is generally carried out in
a mechanically stirring or rocking batch reactor at the Soybean (US) 11.9 0.3 4.1 23.2 54.2 6.3
solvent’s critical temperature and pressure.[16] SFE is Palm (Malaysia) 42.6 0.3 4.4 40.5 10.1 0.2
attracting a great deal of interest because the technique Rapeseed (EU) 3.8 0 2.0 62.2 22.0 9.0
can considerably reduce sample preparation time and can Sunflower (EU) 6.4 0.1 2.9 17.7 72.9 0
provide analyte recovery from solid and semisolid samples Cottonseed 28.7 0 0.9 13.0 57.4 0
that is equal to or better than that of classical extraction (China)
techniques such as Soxhlet extraction. Tallow (US) 23.3 0.1 19.3 42.4 2.9 0.9
Vegetable oils and fats are substances derived from
plants that are composed of triglycerides. Oils extracted Oil (distilled) 16:0 ABI DeABI 18:1 18:2 Diol
from plants have been used in many cultures since ancient
times. The oily seed and nut kernels contain 20–60% oil. Tall oil 38.8 9.7 7.3 23.1 10.4 5.8
The fatty acid compositions of vegetable oils and fats are (Skandinavia)
412 I. KRALOVA AND J. SJÖBLOM

FIG. 1. Crude tall oil (TOME production process).

and inks, and as an emulsifier. The pitch is used as a binder higher viscosity and density, lower heating value and lower
in cement, an adhesive, and an emulsifier for asphalt. cetane number. Problems appear only after the engine has
TOFA is a low-cost alternative to tallow fatty acids for been operating on vegetable oils for longer periods of time,
production of soaps and lubricants. When esterified with especially with direct-injection engines. The problems
pentaerythritol, it is used as a compound of adhesives include: (a) coking and trumpet formation on the injectors
and oil-based varnishes.[18] The pyrolyzate had lower to such an extent that fuel atomization does not occur
viscosity, pour point, and flash point than D2 fuel and properly or is even prevented as a result of plugged orifices,
equivalent heating values.[11] (b) carbon deposits, (c) oil ring sticking, and (d) thickening
The advantages of vegetable oils as diesel fuel are port- and gelling of the lubricating oil as a result of contami-
ability, availability, renewability, higher heat content nation by the vegetable oils.[4]
(about 88% of D2 fuel), lower sulphur and aromatic The direct use of vegetable oils and=or oil blends is
content, biodegrability.[19] Full combustion of a fuel generally considered to be unsatisfactory and impractical
requires in existence the amount of stoichiometric oxygen. for both direct injection and indirect type diesel engines
However, the amount of stochiometric oxygen generally because of their high viscosities and low volatilities injector
is not enough for full combustion because the fuel is not coking and trumpet formation on the injectors, higher level
oxygenated. The structural oxygen content of fuel increases of carbon deposits, oil ring sticking, and thickening and
the combustion efficiency of the fuel due to increased mix- gelling of the engine lubricant oil, acid composition (the
ing of oxygen with the fuel during combustion. For these reactivity of unsaturated hydrocarbon chains), and free
reasons, the combustion efficiency and cetane number of fatty acid content.[20–22] Consequently, different methods
vegetable oil are higher than those of diesel fuel, and the have been considered to reduce the viscosity of vegetable
combustion efficiency of methanol and ethanol is higher oils such as dilution, microemulsification, pyrolysis,
than that of gasoline. The disadvantages of vegetable oils catalytic cracking, and transesterification.
as diesel fuel are visible from Table 3, where we can notice

OIL REFINING TECHNOLOGIES

TABLE 3 Crude vegetable oils contain trace amounts of naturally
Comparison of some fuel properties of vegetable occurring materials such as proteinaceous material, free
oils with D2 fuel fatty acids, and phosphatides. The purpose of caustic
refining is to remove free fatty acids, phosphatides, and
Heating Viscosity other materials including protein meal, glycerol, carbohy-
value Density at 300 K Cetane drates, resins, and metals. Crude vegetable oils obtained
Fuel type (MJ=kg) (kg=m3) (mm2=s) number by oil seed processes have to be refined to remove undesir-
able substances. The typical oil refining process includes
D2 fuel 43.4 815 4.3 47.0 degumming, chemical or physical refining, bleaching,
Sunflower oil 39.5 918 58.5 37.1 vinterization, and deodorization. Deodorization is an
Cottonseed oil 39.6 912 50.1 48.1 important step in the oil refining process. During this step,
Soybean oil 39.6 914 65.4 38.0 steam at 1 to 6 mm Hg pressure is injected into the oil at
Corn oil 37.8 915 46.3 37.6 490 to 550 K to eliminate free fatty acids, aldehydes,
Opium poppy oil 38.9 921 56.1 – unsaturated hydrocarbons, and ketones, which cause
Rapeseed oil 37.6 914 39.2 37.6 undesirable odors and flavors in the oil.[23] Soap stock
BIOFUELS 413

and other impurities are separated from the oil by mixed triglycerides makes pyrolysis reactions more
centrifuges. Caustic soda is not completely selective in complicated.[30] Generally, thermal decomposition of tri-
reacting with free fatty acids and phosphatides; therefore, glycerides proceeds through either a free-radical or carbo-
some triglycerides are hydrolyzed and saponified (broken nium ion mechanism.[21] Vegetable oil is converted into
down and converted into soap. Recycling and refining are lower molecular products by two simultaneous reactions:
the applicable processes for upgrading of vegetable oils cracking and condensation. The heavy hydrocarbons
by converting them into reusable products such as gasoline produced from primary and secondary deoxygenation
and diesel fuel. Possible acceptable processes are trans- and cracking yield light olefins and light paraffins, water,
esterification, cracking, and pyrolysis.[24,25] carbon dioxide, and carbon monoxide. Hydrocarbon for-
mation can be identified as deoxygenation, cracking, and
aromatization with H-transfer. Deoxygenation can take
PYROLYSIS AND CRACKING place via decarboxylation and dehydration.[31] The distri-
Because of the possibility of producing triglycerides in a bution of pyrolysis products depends on the dynamics
wide variety of products by high-temperature pyrolysis and kinetic control of different reactions. The maximum
reactions, many investigators have studied the pyrolysis gasoline fraction can be obtained under appropriate reac-
of triglycerides to obtain products (liquid, gas, and solid) tion conditions. Thermodynamic calculation shows that
suitable for fuel under different reaction conditions with the initial decomposition of vegetable oils occurs with the
and without catalyst.[26–29] Pyrolysis is the thermal breaking of CO bonds at lower temperatures, and fatty
degradation of vegetable oils by heat in the absence of acids are the main product. The pyrolysis temperature
oxygen, which results in the production of alkanes, alkenes, should be higher than 675 K; at this temperature, the
alkadienes, carboxylic acids, aromatics, and small amounts maximum diesel yield with high oxygen content can be
of gaseous products. Depending on the operating con- obtained.[30] In pyrolysis, the high-molecular-weight
ditions, the pyrolysis process can be divided into three materials are heated to high temperatures, so their
subclasses: conventional pyrolysis, fast pyrolysis, and flash macromolecular structures are broken down into smaller
pyrolysis. The conversion of oil was high (42–83 wt%) and molecules and a wide range of hydrocarbons are formed.
the product distribution depended strongly on the reaction These pyrolytic products can be divided into a gas fraction,
temperature, residence times, and catalyst content. The a liquid fraction consisting of paraffins, olefins and
pyrolysis products consisted of gas and liquid hydrocar- naphthenes, and solid residue.[32] The cracking process
bons, carboxylic acids, CO, CO2, H2, and water.[27] The yields a highly unstable low-grade fuel oil that can be
three vegetable oils (soybean, palm, and castor oils) were acid-corrosive, tarry, and discolored along with a charac-
pyrolyzed to obtain light fuel products at 503 to teristically foul odor.[33] It was proposed that thermal and
673 K.[29] Palm oil reacts in a lower temperature range with catalytic cracking of triglyceride molecules occurs at the
a higher yield in the heavy fraction. A short pyrolysis time external surface of the catalysts to produce small
(less than 10 seconds) leads to a high amount of alkanes, molecular size components, comprised mainly of heavy
alkenes, and aldehydes instead of carboxylic acids. On liquid hydrocarbons and oxygenates.[34] In general, it is
the other hand, higher temperature and long pyrolysis assumed that the reactions occur predominantly within
times do not favor as pyrolysis of this material. Increasing the internal pore structure of a zeolite catalyst. The catalyst
Na2CO3 content and temperature increases the formation acidity and pore size affect the formation of aromatic
of liquid hydrocarbon and gas products and decreases and aliphatic hydrocarbons. Hydrogen transfer reactions,
the formation of aqueous-phase, acid-phase, and coke– essential for hydrocarbon formation, are known to increase
residual oil. The highest C5–C11 yield (36.4%) was obtained with catalyst acidity. The high acid density of ZnCl2 cata-
using 10% Na2CO3 and a packed column of 180 mm at lysts contribute greatly to high amounts of hydrocarbons
693 K. The HHV of pyrolysis oil from rapeseed in the liquid product.
(38.4 MJ=kg) is slightly lower than that of gasoline The thermal degradation of aliphatic long-chain com-
(47 MJ=kg), diesel fuel (43 MJ=kg), or petroleum pounds is known as cracking. Higher-molecular-weight
(42 MJ=kg) but higher than coal (32–37 MJ=kg). The pyro- molecules generally convert into smaller-molecular weight
lyzate had a lower viscosity, pour point, and flash point molecules by the cracking process. Palm oil and copra oil
than D2 fuel and equivalent heating values.[11] Vegetable was subjected to conversion over different catalysts like
oils contain mainly palmitic, stearic, oleic, and linoleic silica-alumina and zeolite.[35] It was found that the conver-
acids. These fatty acids underwent various reactions, sion of palm and copra oil was 84 wt% and 74 wt%, respect-
resulting in the formation of different types of hydrocar- ively. The silica-alumina catalyst was highly selective for
bons. The variety of reaction paths and intermediates obtaining aliphatic hydrocarbons, mainly in the kerosene
makes it difficult to describe the reaction mechanism. boiling point range.[36] The organic liquid products
In addition, the multiplicity of possible reactions of obtained with a silica-alumina catalyst contained between
414 I. KRALOVA AND J. SJÖBLOM

4 and 31 wt% aliphatic hydrocarbons and 14 and 58 wt% This is a major reason why neat vegetable oils have largely
aromatic hydrocarbons. The conversion was high and ran- been abandoned as alternative diesel fuels in favor of
ged between 81 and 99 wt%. Silica-alumina catalysts are monoalkyl esters such as methyl esters. FAME of vegetable
suitable for converting vegetable oils into aliphatic hydro- oils and fats has cloud point upper zero (reason for blend-
carbons. Zinc chloride catalyst, as a Lewis acid, contribu- ing in ratio with petrodiesel) and main disadvantage for
ted to hydrogen transfer reactions and the formation of using them in cold conditions, but this is improved in case
hydrocarbons in the liquid phase. Palm oil was converted of tall oil methyl ester which has this cloud point below
into hydrocarbons using a shape selective zeolite cata- zero, usually around 2 C. Several aspects, including the
lyst.[34] Palm oil can be converted into gasoline, diesel type of catalyst (alkaline, acid, or enzyme), alcohol=
and kerosene, light gases, coke and water with a yield of vegetable oil molar ratio, temperature, purity of the reac-
70 wt%. The maximum yield of gasoline-range hydrocar- tants (mainly water content), and free fatty acid content
bons was 40 wt% of the total product. The maximum con- have an influence on the course of transesterification. In
version of palm oil, 99 wt%, and gasoline yield of 48 wt% the conventional transesterification of fats and vegetable
was obtained with composite micromesoporous zeolite.[37] oils for biodiesel production, free fatty acids and water
always produce negative effects.[39] Transesterification is
an equilibrium reaction, and the transformation occurs
TRANSESTERIFICATION—METHOD FOR
essentially by mixing the reactants. In the transesterifica-
PRODUCTION BIODIESELS FROM TRIGLYCERIDES
tion of vegetable oils, a triglyceride reacts with an alcohol
One of the most common methods used to reduce oil in the presence of a strong acid or base, producing a mix-
viscosity in the biodiesel industry is called transesterifica- ture of fatty acids, alkyl esters, and glycerol. The stoichio-
tion.[11] Transesterification (also called alcoholysis) is the metric reaction requires 1 mol of a triglyceride and 3 mol of
reaction of a fat or oil triglyceride with an alcohol to form the alcohol. However, an excess of the alcohol is used to
esters and glycerol. Because the reaction is reversible, increase the yields of the alkyl esters and to allow their
excess alcohol is used to shift the equilibrium to the pro- phase separation from the glycerol formed.
duct side. Figure 2 shows enzymatic biodiesel production Various studies have been carried out using different oils
by interesterification with methyl acetate in the presence of as raw material, different alcohols (methanol, ethanol,
lipase enzyme as catalyst.[4] The biodiesel reaction requires butanol), as well as different catalysts, including
a catalyst such as sodium hydroxide to split the oil mole- homogeneous ones such as sodium hydroxide, potassium
cules and an alcohol (methanol or ethanol) to combine hydroxide, sulfuric acid, and supercritical fluids and
with the separated esters. The main byproduct is glycerine. heterogeneous ones such as lipases.[40] A novel process of
A catalyst is usually used to improve the reaction rate and biodiesel fuel production has been developed by a non-
yield. The transesterification reaction proceeds well in the catalytic supercritical methanol method. Supercritical
presence of some homogeneous catalysts such as potassium methanol is believed to solve the problems associated with
hydroxide (KOH) and sodium hydroxide (NaOH) and sul- the two-phase nature of normal methanol=oil mixtures by
furic acid or heterogeneous catalysts such as metal oxides forming a single phase as a result of the lower value of the
or carbonates. Transesterification is the process of dielectric constant of methanol in the supercritical state.
exchanging the alkoxy group of an ester compound by The supercritical methanol process is noncatalytic, involves
another alcohol. These reactions are often catalyzed by a much simpler purification of products, has a lower reac-
the addition of a base and acid. Bases can catalyze the reac- tion time, is more environmentally friendly, and requires
tion by removing a proton from the alcohol, thus making it lower energy use. However, the reaction requires tempera-
more reactive, while acids can catalyze the reaction by tures of 525 to 675 K and pressures of 35 to 60 MPa.[19,41]
donating a proton to the carbonyl group, thus making it
more reactive.[38] The physical properties of the primary
chemical products of transesterification are given in CATALYTIC TRANSESTERIFICATION METHODS
Table 4. The high viscosity of vegetable oils was the cause As was mentioned, transesterification process is cata-
of severe operational problems such as engine deposits. lyzed by Brønsted acids, preferably by sulfonic and sulfuric

FIG. 2. Enzymatic biodiesel production by interesterification with methyl acetate.

BIOFUELS 415

TABLE 4
Comparison of physical properties of vegetable oils and their methylesters prepared via transesterification
Oil or fat (refined) Methyl ester

Viscosity Cetane Flash point Viscosity Cetane Flash point

(mm2=s at 311 K) number (K) (mm2=s at 311 K) number (K)
Properties
Soybean (US) 33.1 38.1 548 4.08 46 441
Palm (Malaysia) 42.7 65 573 3.94 62 431
Rapeseed (EU) 37.3 37.5 531 4.60 47 453
Sunflower (EU) 34.4 36.7 535 4.16 49 439
Cottonseed (China) 33.7 37.1 524 3.75 42 433
Tallow (US) 32.3 75 525 4.10 58 436
Tall oil (Scandinavia) 51.0 ? 485 5.30 50 461

acids. These catalysts give very high yields in alkyl esters, conditions resulted in adequate yield of biodiesel in the case
but the reactions are slow. The alcohol=vegetable oil molar of the enzyme-based process.
ratio is one of the main factors that influence transesterifi-
cation. An excess of the alcohol favors the formation of
alkyl esters. On the other hand, an excessive amount of NONCATALYTIC SUPERCRITICAL METHANOL
alcohol makes the recovery of the glycerol difficult, so that TRANSESTERIFICATION
the ideal alcohol=oil ratio has to be established empirically. Noncatalytic supercritical methanol transesterification is
Each step in the process is reversible, but in the presence of performed in a stainless steel cylindrical reactor (autoclave)
a large excess of the alcohol, the equilibrium point of the at 520 K.[47] The most important variables affecting the
reaction is displaced so that esterification proceeds virtually methyl ester yield during transesterification reaction are
to completion. In the alkali catalytic methanol transesteri- molar ratio of alcohol to vegetable oil and reaction tem-
fication method, the catalyst (KOH or NaOH) is dissolved perature. Viscosities of the methyl esters from the vegetable
into methanol by vigorous stirring in a small reactor. The oils were slightly higher than that of D2 fuel. Higher molar
oil is transferred into a biodiesel reactor and then the ratios result in greater ester production in a shorter time.
catalyst=alcohol mixture is pumped into the oil. The result- The supercritical methanol process is noncatalytic, involves
ing biodiesel fuel when used directly in a diesel engine will simpler purification, has a lower reaction time, and is less
burn up to 75% cleaner than petroleum D2 fuel. The energy intensive. Therefore, supercritical methanol method
base-catalyzed transesterification of vegetable oils proceeds would be more effective and efficient than the common
faster than the acid-catalyzed reaction. Alkaline metal commercial process.[39] The parameters affecting methyl
hydroxides, such as KOH and NaOH, are cheaper than ester formation are reaction temperature, pressure, molar
metal alkoxides, but less active. The presence of water gives ratio, water content, and free fatty acid content. It is evi-
rise to hydrolysis of some of the produced ester, with dent that at subcritical states of alcohol, the reaction rate
consequent soap formation. is so low and gradually increased as either pressure or tem-
Biodiesel can be obtained from biocatalytic transesterifi- perature rises. It was observed that increasing the reaction
cation methods.[42–44] Methyl acetate, a novel acyl acceptor temperature, especially to supercritical conditions, had a
for biodiesel production, has been developed, and a favorable influence on the yield of ester conversion. The
comparative study on Novozym 435-catalyzed transesteri- yield of alkyl ester increased when the molar ratio of oil
fication of soybean oil for biodiesel production with differ- to alcohol was increased.[47] In the supercritical alcohol
ent acyl acceptors was studied.[45] transesterification method, the yield of conversion rises
There were tested also various types of lipases. Only 50 to 95% for the first 10 minutes.
lipase from Chromobacterium viscosum was found to give Water content is an important factor in the conventional
appreciable yield.[46] Immobilization of lipase (Chromo- catalytic transesterification of vegetable oil. In the conven-
bacterium viscosum) on Celite-545 enhanced the biodiesel tional transesterification of fats and vegetable oils for bio-
yield to 71% from the 62% yield obtained by using free diesel production, free fatty acids and water always
tuned enzyme preparation with a process time of 8 hours produce negative effects since the presence of free fatty
at 113 K. Immobilized Chromobacterium viscosum lipase acids and water causes soap formation, consumes catalyst,
can be used for ethanolysis of oil. It was seen that immobi- and reduces catalyst effectiveness like is visible from
lization of lipases and optimization of transesterification Figures 3 and 4.[39] The critical temperature and the critical
416 I. KRALOVA AND J. SJÖBLOM

FIG. 3. Yields of methyl esters as a function of water content in transesterification of triglycerides.

pressure of methanol are 516.2 K and 6.4 MPa, respect- . Conversion of the oil into its fatty acids and then
ively. The sunflower seed oil was transesterified 1:1, 1:3, into biodiesel
1:9, 1:20, and 1:40 vegetable oil-ethanol molar ratios in . Noncatalytic transesterification of oils and fats.
supercritical ethanol conditions. It was observed that
Biodiesel produced by transesterification reactions
increasing molar ratio had a favorable influence on ester
can be alkali catalyzed, acid catalyzed, or enzyme cata-
conversion.[11] But it is obvious from last studies that we
lyzed, but the first two types have received more attention
can use catalyst in supercritical methanol transesterifica-
because of the short reaction times and low cost compared
tion where the yield of conversion rises to 60 to 90% for
with the third one.[49] Most of the biodiesel produced
the first minute.[48] This process is carried out in an auto-
today is made with the base catalyzed reaction for several
clave in the presence of 1–5% NaOH, CaO, and MgO as
reasons:
catalyst at 520 K.
. It involves low temperature and pressure.
. It yields high conversion (98%) with minimal side
CURRENT TECHNOLOGIES IN BIODIESEL
reactions and reaction time.
PRODUCTION . It allows a direct conversion into biodiesel with no
Biodiesel as it is defined today is obtained by transester- intermediate compounds.
ifying triglycerides with methanol. Methanol is the . It requires simple construction materials.
preferred alcohol for obtaining biodiesel because it is the
cheapest alcohol. Base catalysts are more effective than The base-catalyzed production of biodiesel generally
acid catalysts and enzymes.[4] occurs using the following steps:
The production processes for biodiesel are well known. . Mixing of alcohol and catalyst
There are four basic routes to biodiesel production from . Transesterification reaction
oils and fats: . Separation
. Base-catalyzed transesterification . Biodiesel washing
. Direct acid-catalyzed transesterification . Alcohol removal

FIG. 4. Yields of methyl esters as a function of free fatty acid content in biodiesel production.
BIOFUELS 417

. Glycerine neutralization fatty acid such as oleic acid is used to produce biodiesel, the
. Product quality alkali catalyst typically used to encourage the reaction will
react with this acid to form soap. Excessive soap in the pro-
The basic catalyst is typically sodium hydroxide (caustic
ducts can inhibit later processing of the biodiesel, including
soda) or potassium hydroxide (caustic potash). Recom-
glycerol separation and water washing. Water in the oil or
mended reaction time varies from 1 to 8 hours, and optimal
fat can also be a problem.[50] Water and alcohol are
reaction time is about 2 hours.[50] Excess alcohol is nor-
removed to produce 90% pure glycerine that is ready to
mally used to ensure total conversion of the fat or oil into
be sold as crude glycerine.
its esters. After the reaction is complete, two major pro-
The most important aspects of biodiesel production to
ducts form: glycerine and biodiesel. The glycerine phase
ensure trouble-free operation in diesel engines are:
is much denser than the biodiesel phase and the two can
be gravity separated with glycerine simply drawn off the . Complete transesterification reaction
bottom of the settling vessel. In some cases, a centrifuge . Removal of glycerine
is used to separate the two materials faster. The biodiesel . Removal of catalyst
product is sometimes purified by washing gently with warm . Removal of alcohol
water to remove residual catalyst or soaps, dried, and sent . Removal of free fatty acids
to storage.[4,47] For an alkali catalyzed transesterification,
These parameters are all specified through the biodiesel
the triglycerides and alcohol must be substantially anhy-
standard, ASTM D 6751 which are essential for further
drous because water makes the reaction partially change
commercial use. This standard identifies the parameters
to saponification, which produces soap. The soap lowers
the pure biodiesel (B100) must meet before being used as
the yield of esters and renders the separation of ester and
a pure fuel or being blended with petroleum-based diesel
glycerol and the water washing difficult. Low free fatty acid
fuel. Biodiesel, B100, specifications (ASTM D 6751–02
content in triglycerides is required for alkali-catalyzed
requirements) are given in Table 5. The EN 14214 is an
transesterification. When an alkali catalyst is present, the
international standard that describes the minimum require-
free fatty acid will react with alkali catalyst to form soap.
ments for biodiesel produced from rapeseed fuel stock (also
It is common for oils and fats to contain trace amounts
known as rapeseed methyl esters). Table 6 shows inter-
of water. When water is present in the reaction, it generally
national standard (EN 14214) requirements for biodiesel.
manifests itself through excessive soap production. The
soaps of saturated fatty acids tend to solidify at ambient
temperatures, so a reaction mixture with excessive soap Biodiesel Production with Batch Processing
may gel and form a semisolid mass that is very difficult The simplest method for producing alcohol esters is to
to recover. When water is present, particularly at high tem- use a batch, stirred tank reactor. Alcohol-to-triglyceride
peratures, it can hydrolyze the triglycerides to diglycerides ratios from 4:1 to 20:1 (mole:mole) have been reported,
and form a free fatty acid. If an oil or fat containing a free with a 6:1 ratio most common. The reactor may be sealed

TABLE 5
Biodiesel, B100, specifications (ASTM D6751–02 requirements)
Property Method Limits Units

Flash point D93 130 min C
Water and sediment D2709 0.050 max % volume
Kinematic viscosity at 40 C D445 1.9–6.0 mm2=s
Sulfated ash D874 0.020 max wt.%
Total sulfur D5453 0.05 max wt.%
Copper strip corrosion D130 No. 3 max
Cetane number D613 47 min

Cloud point D2500 Report C
Carbon residue D4530 0.050 max wt.%
Acid number D664 0.80 max mg KOH=g
Free glycerine D6584 0.020 wt.%
Total glycerine D6584 0.240 wt.%
Phosphorus D4951 0.0010 wt.%
Vacuum distillation end point D1160 360 C max, at 90% distilled
C
418 I. KRALOVA AND J. SJÖBLOM

TABLE 6
International standard (EN 14214) requirements for biodiesel
Property Units Lower limit Upper limit Test-method

Ester content % (m=m) 96.5 – Pr EN 14103d

Density at 15 C kg=m3 860 900 EN ISO 3675=EN ISO 12185
Viscosity at 40 C mm2=s 3.5 5.0 EN ISO 3104

Flash point C >101 – ISO CD 3679e
Sulfur content mg=kg – 10 –
Tar remnant (at 10% distillation remnant) % (m=m) – 0.3 EN ISO 10370
Cetane number – 51.0 – EN ISO 5165
Sulfated ash content % (m=m) – 0.02 ISO 3987
Water content mg=kg – 500 EN ISO 12937
Total contamination mg=kg – 24 EN 12662
Copper band corrosion (3 h at 50 C) rating Class 1 Class 1 EN ISO 2160
Oxidation stability at 110 C hours 6 – pr EN 14112k
Acid value mg KOH=g – 0.5 pr EN 14104
Iodine value – – 120 pr EN 14111
Linoleic acid methyl ester % (m=m) – 12 pr EN 14103d
Polyunsaturated (4 double bonds) % (m=m) – 1 –
methylester
Methanol content % (m=m) – 0.2 pr EN 141101
Monoglyceride content % (m=m) – 0.8 pr EN 14105m
Diglyceride content % (m=m) – 0.2 pr EN 14105m
Triglyceride content % (m=m) – 0.2 pr EN 14105m
Free glycerine % (m=m) – 0.02 pr EN 14105m=pr EN 14106
Total glycerine % (m=m) – 0.25 pr EN 14105m
Alkali metals (Na þ K) mg=kg – 5 pr EN 14108=pr EN 14109
Phosphorus content mg=kg – 10 pr EN 14107p

or equipped with a reflux condenser. The operating tem- Biodiesel Production with Continuous Process
perature is usually about 340 K, although temperatures Conventionally, transesterification can be performed
from 298 K to 358 K have been reported.[4,11,47,49,51,52] using alkaline, acid, or enzyme catalysts.[4,53,54] As alkali-
The most commonly used catalyst is sodium hydroxide, catalyzed systems are very sensitive to both water and free
though potassium hydroxide also used. Typical catalyst fatty acid content, the glycerides and alcohol must be
loadings range from 0.3% to about 1.5%. Transesterifica- substantially anhydrous because water makes the reaction
tion completion rates of 85 to 95% have been reported.
Typical reaction times range from 20 minutes to more
than 1 hours. In transesterification the oil is first added to
the system, followed by the catalyst and methanol. The sys-
tem is agitated during the reaction time. Then agitation is
stopped. In some processes, the reaction mixture is allowed
to settle in the reactor to give an initial separation of the
esters and glycerol. In other processes the reaction mixture
is pumped into a settling vessel or is separated using a cen-
trifuge. Figure 5 shows the sketch of such batch processes.[50]
The alcohol is removed from both the glycerol and ester
stream using an evaporator or a flash unit. The esters are
neutralized, washed gently using warm, slightly acidic water
to remove residual methanol and salts, and then dried. The
finished biodiesel is then transferred to storage. The glycerol
stream is neutralized and washed with soft water. The gly- FIG. 5. Simplified flow diagram of base-catalyzed biodiesel
cerol is then sent to the glycerol refining unit. processing.
BIOFUELS 419

FIG. 6. Flowsheet of reactive distillation.

partially change to saponification, which produces soaps, continuous process and is not feedstock specific. The
thus consuming the catalyst and reducing the catalytic unique feature of the BIOX process is that it uses inert
efficiency, as well as causing an increase in viscosity, forma- reclaimable cosolvents in a single-pass reaction taking only
tion of gels, and difficulty in separations. There are several seconds at ambient temperature and pressure. The BIOX
processes that use intense mixing, either from pumps or process handles not only grain-based feedstocks but also
motionless mixers, to initiate the esterification reaction. A waste cooking greases and animal fats.[50] The BIOX pro-
popular variation of the batch process which needs high cess uses a cosolvent, tetrahydrofuran, to solubilize the
alcohol=acid ratio (several separation problems and high methanol. Cosolvent options are designed to overcome
corrosivity and toxicity) is the use of continuous stirred slow reaction times caused by the extremely low solubility
tank reactors in series.[77] Instead of allowing time for the of the alcohol in the triglyceride phase like is shown in
reaction in an agitated tank, the reactor is tubular. The Figure 7.[50]
result is a continuous system that requires rather short resi- A novel process of biodiesel fuel production has been
dence times, as low as 6 to 10 minutes, for near completion developed by a noncatalytic supercritical methanol
of the reaction. This continuous process is heterogeneous method. Supercritical methanol is believed to solve the
and is based on reactive distillation (Figure 6). Easy separ- problems associated with the two-phase nature of normal
ation and environmental friendly process belong to main methanol=oil mixtures by forming a single phase as a result
advantages of whole process. The key factor is the selection of the lower value of the dielectric constant of methanol in
of the right and effective solid catalyst which leads to the supercritical state. As a result, the reaction was found
reduction of energy consumption and investments at all. to be complete in a very short time.[55] In contrast to cata-
lytic processes under barometric pressure, the supercritical
Biodiesel Production with Noncatalyzed
Transesterification
There are two noncatalyzed transesterification pro-
cesses. These are the BIOX process and the supercritical
alcohol (methanol) process. The BIOX process is a new
Canadian process. Production process was transformed
through the selection of inert cosolvents that generate an
oil-rich one-phase system. This reaction is over 99% com-
plete in seconds at ambient temperatures, compared to pre-
vious processes that required several hours. Process uses
base-catalyzed transesterification (specifically transmethyl-
ation) of fatty acids to produce methyl esters. It is a FIG. 7. BIOX cosolvent process.
420 I. KRALOVA AND J. SJÖBLOM

esters decrease sharply following the transesterification

process. The viscosity of D2 fuel is 2.7 mm2=s at
311 K.[19] Compared to D2 fuel, all of the vegetable oil
methyl esters are slightly viscous. The flash point values
of vegetable oil methyl esters are much lower than those
of vegetable oils. An increase in density from 860 to
885 kg=m3 for vegetable oil methyl esters or biodiesels
increases the viscosity from 3.59 to 4.63 mm2=s, and the
increases are highly regular.
FIG. 8. Supercritical transesterification process.
CETANE NUMBER, CLOUD POINT, AND POUR POINT
methanol process is noncatalytic, involves much simpler The cetane number is a measure of ignition quality or
purification of products, has a lower reaction time, is more ignition delay and is related to the time for a liquid fuel to
environmentally friendly, and requires lower energy use ignite after injection into a compression engine. The cetane
(Figure 8).[50] However, the reaction requires temperatures number (CN) is based on two compounds, hexadecane, with
of 525 to 675 K and pressures of 35 to 60 MPa.[19,39] Com- a CN of 100, and heptamethylnonane, with a CN of 15. The
pared with the alkali-catalyzed method, the supercritical CN of biodiesel is generally higher than conventional diesel.
methanol method has advantages in terms of reaction time The longer the fatty acid carbon chains and the more satu-
and purification step. rated the molecules, the higher the CN. The CN of biodiesel
from animal fats is higher than those of vegetable oils.[11]
FUEL PROPERTIES OF BIODIESEL Two important parameters for low-temperature applica-
tions of a fuel are cloud point (CP) and pour point (PP).
Biodiesels are characterized by their viscosity, density,
The CP is the temperature at which wax first becomes visible
cetane number, cloud and pour points, distillation range,
when the fuel is cooled. The PP is the temperature at which
flash point, ash content, sulfur content, carbon residue,
the amount of wax from a solution is sufficient to gel the
acid value, copper corrosion, and higher heating value
fuel; thus it is the lowest temperature at which the fuel can
(HHV). The flash point values of vegetable oil methyl
flow. Biodiesel has a higher CP and PP compared to conven-
esters are significantly lower than those of vegetable oils.
tional diesel.[57] The CN scale shows that straight-chain,
There is high regression between the density and viscosity
saturated hydrocarbons have higher CNs compared to
values of vegetable oil methyl esters. The relationships
branched-chain or aromatic compounds of similar molecu-
between viscosity and flash point for vegetable oil methyl
lar weight and number of carbon atoms. The CN is one of
esters are considerably regular.
the prime indicators of the quality of diesel fuel.
The physical and chemical properties and the perform-
VISCOSITY, DENSITY AND FLASH POINT ance of ethyl esters are comparable to those of methyl esters.
Viscosity is the most important property of biodiesels Methyl and ethyl esters have almost the same heat content.
since it affects the operation of fuel injection equipment, The viscosities of ethyl esters are slightly higher and the cloud
particularly at low temperatures when an increase in vis- and pour points are slightly lower than those of methyl
cosity affects the fluidity of the fuel. High viscosity leads esters. Engine test demonstrated that methyl esters produced
to poorer atomization of the fuel spray and less accurate slightly higher power and torque than ethyl esters.[58] The
operation of the fuel injectors. The lower the viscosity of ethyl esters tend to have more injector coking than the
the biodiesel, the easier it is to pump and atomize and methyl esters. Methanol is considerably easier to recover
achieve finer droplets.[56] Biodiesels have a viscosity close than ethanol. Ethanol forms azeotrope with water so it is
to that of diesel fuels. As the oil temperature increases its expensive to purify ethanol during recovery. If the water is
viscosity decreases. Table 4 below shows comparison of not removed, it will interfere with the reactions. Methanol
some fuel properties of vegetable oils and their methyl ester recycles easier because it does not form an azeotrope. These
given by different researchers. The major problem associa- two factors are the reason that, even though methanol is
ted with the use of pure vegetable oils as fuels for diesel more toxic, it is the preferred alcohol for producing biodiesel.
engines is high fuel viscosity in the compression ignition.
Therefore, vegetable oils are converted into their methyl
esters (biodiesel) by transesterification. The viscosity values COMBUSTION PROPERTIES AND CHARACTERISTIC
of vegetable oils are between 27.2 and 53.6 mm2=s, whereas Combustion represents a chemical reaction during
those of vegetable oil methyl esters are between 3.6 and which from certain matters other simple matters are
4.6 mm2=s. The viscosity values of vegetable oil methyl produced, this is a combination of inflammable matter with
BIOFUELS 421

oxygen of the air accompanied by heat release. During

heating it evaporates together with a part of carbon in
the form of hydrocarbons, combustible gases, and CO
released by thermal degradation of the fuel. The combus-
tion process is started by heating the fuel above its ignition
temperature in the presence of oxygen or air. Under the
influence of heat, the chemical bonds of the fuel are
cleaved. If complete combustion occurs, the combustible
elements (C, H, and S) react with the oxygen content of
the air to form CO2, H2O, and mainly SO2. If not enough
oxygen is present or the fuel and air mixture is insufficient,
then the burning gases are partially cooled below the
ignition temperature and the combustion process stays
incomplete. The gases then still contain combustible com-
ponents, mainly carbon monoxide (CO), unburned carbon
(C), and various hydrocarbons (CxHy).
The structural oxygen content of a fuel improves its com- FIG. 9. Percentage change in exhaust emissions in vegetable oil based
biodiesels.
bustion efficiency due to an increase in the homogeneity of
oxygen with the fuel during combustion. Because of this
the combustion efficiency of biodiesel is higher than that emission rates reflects the changes in the total carbon con-
of petrodiesel, and the combustion efficiency of methanol= tents of the two fuels consumed per unit time. However, it
ethanol is higher than that of gasoline. Biodiesel contains produces larger quantities of CO2 than conventional fuels,
11% oxygen by weight and no sulfur. The higher oxygen but as most of this is from renewable carbon stocks that
content encourages more complete combustion. Neat bio- fraction is not counted towards the greenhouse gas emis-
diesel generally contains 10–11% oxygen, and B35 contains sions from the fuel.[61] There are several other studies about
4% oxygen. Petroleum diesel contains almost no oxygen. relative CO2 flow reduction. Tan et al. reported several
The overall test results showed that B35 reduced CO emis- CO2 scenarios based on coconut methyl ester with cogen-
sions by an average of about 12%.[59] The use of biodiesel eration option using residual biomass.[62] Other studies
can extend the life of diesel engines because it is more report a 78% reduction in CO2 emissions for soybean oil
lubricating than petroleum diesel fuel. Biodiesel has better methyl ester relative to conventional diesel under North
lubricant properties than petrodiesel. The higher heating American conditions.[63] The GREET 1.5a model[64] pre-
values (HHVs) of biodiesels are relatively high. The HHVs dicts results for B20, a blend containing 20% soybean oil
of biodiesels (39–41 MJ=kg) is slightly lower than that of methyl ester and 80% petroleum diesel. When extrapolated
gasoline (46 MJ=kg), petrodiesel (43 MJ=kg), or petroleum to pure biodiesel, these results indicate a reduction of 55%
(42 MJ=kg), but higher than coal (32–37 MJ=kg). relative to reformulated diesel. A more recent Australian
The combustion of biodiesel alone provides over a 90% study[61] estimates the reduction at 57–66% for biodiesel
reduction in total unburned hydrocarbons and a 75–90% derived from canola oil. This study assumed that
reduction in polycyclic aromatic hydrocarbons. Biodiesel biomass-derived ethanol was used instead of methanol
further provides significant reductions in particulates and for transesterification. Rapeseed oil methyl ester was also
carbon monoxide than petroleum diesel fuel (Figure 9).[76] analyzed by Kaltschmitt et al. under European conditions,
Biodiesel belongs to climate friendly fuels, even when con- with results showing a 66% improvement over petroleum
sidered on a life-cycle basis, because has the lowest exbo- diesel.[65] Mean annual production of coconut oil in the
died greenhouse gas emissions (in grams greenhouse gases Philippines through the 1990s was 1.31 106 tons based
per kilometer traveled). Biodiesel contains 80% by mass on data from the FAO (Food & Agriculture Organization
of carbon, then each kilogram of biodiesel can generate of the United Nations) Statistical Database. This quantity
2.935 kg of CO2 and each kilogram of methanol can gener- is sufficient to displace only 8.26% of the projected
ate 1.375 kg of CO2, assuming that all the carbon contents 6.03 1017 J diesel fuel requirement in 2010. Utilization
of the two fuels are converted into CO2.[60] The results indi- of all available coconut resources for the biodiesel program
cate that the maximum CO2 mass emission rate would can reduce projected 2010 combustion-related CO2 emis-
increase from 12.77 kg=hours at zero fumigation ratio to sions of 130 106 tons per annum by up to 3.85%.
14.34 kg=h at the fumigation ratio of 0.55, when operating The major disadvantages of biodiesel are its higher vis-
at 0.19 MPa; while, at the other two engine loads, the cosity, lower energy content, higher cloud point and pour
changes in the maximum CO2 mass emission rates would point, higher nitrogen oxide (NOx) emissions, lower engine
be insignificant. The difference in the maximum CO2 mass speed and power, injector coking, engine compatibility,
422 I. KRALOVA AND J. SJÖBLOM

high price, and higher engine wear. Important operating requirements for heavy-duty engine emissions certification
disadvantages of biodiesel in comparison with petrodiesel testing as specified in Code of Federal Regulations Title
are cold start problems, lower energy content, higher cop- 40, Part 86, Subpart N. The fuel system was flushed before
per strip corrosion, and fuel pumping difficulty from higher changing from biodiesel to certification diesel. Separate
viscosity. Taking into account the higher production value fuel filters were used for biodiesel and certification diesel
of biodiesel as compared to petrodiesel, this increase in fuel to minimize cross contamination. Note that the palmitate
consumption raises in addition the overall cost of appli- (C16:0), stearate (C18:0), and hydrogenated soy fuels have
cation of biodiesel as an alternative to petrodiesel. Biodie- high melting points (are solid at room temperature) and
sel has a higher cloud point and pour point compared to were therefore difficult to work with. To test these fuels
conventional diesel.[57] Neat biodiesel and biodiesel blends they were melted using electric heaters and then poured
increase nitrogen oxide (NOx) emissions compared with into an electrically heated fuel tank. Total hydrocarbon
petroleum-based diesel fuel used in an unmodified diesel was determined by a continuous flame ionization detector,
engine.[66] Biodiesels on average decrease power by 5% NOx by chemiluminescence, and CO by nondispersive IR.
compared to diesel at rated loads.[67] Particulate matter is sampled through a secondary tunnel
that ensures a filtered gas temperature below 52 C (126 F).
Since the PM mass collected for the biodiesel samples was
ENGINE OPERATING TESTS small, even minor differences in filter weight due to water
The exhaust emissions of commercial biodiesel and pet- adsorption can impact the particulate mass emission.
rodiesel were studied in a 2003 model year heavy-duty 14 L The impact of molecular structure is implicit in either
six-cylinder diesel engine with EGR.[5] The commercial the density or cetane number. More saturated esters have
biodiesel fuel significantly reduced PM exhaust emissions higher cetane numbers and lower densities than less satu-
(75–83%) compared to the petrodiesel base fuel. However, rated esters. McCormick et al.[68] studied direct compari-
NOx exhaust emissions increased slightly with commercial sons of fuels with differing numbers of double bonds in
biodiesel compared to the base fuel. Nonsaturation in the the fatty acid chain. They include both fuels prepared from
fatty compounds causes an increase in NOx exhaust emis- pure or nearly pure fatty acids and fuels prepared from
sions.[5] Oxygenated fuels are well-known to reduce exhaust various more practical feedstocks. For fuels containing a
emissions from motor vehicles. In particular, methyl- mixture of molecules, the iodine number is a measure of
tertiary-butyl ether (MTBE) and ethanol reduce emissions the degree of unsaturation or number of double bonds.
from gasoline engines. In high polluting automobiles, oxy- Iodine number has been measured for the pure ester fuels
genated gasoline can decrease carbon monoxide (CO) up to and many of the fuels prepared from more practical feed-
50%. This success of oxygenated gasoline has led to interest stocks. They proved that between iodine number and
in the use of oxygenated compounds as emissions reducing NOx is a highly linear relationship and this regression
additives in diesel fuel. Numerous oxygenated compounds predicts that a biodiesel with an iodine number of 38 will
have been investigated as either diesel fuel additives be NOx neutral relative to certification diesel. This
or replacements and have shown emissions reducing corresponds to an average of 1.5 double bonds=molecule.
properties. Many studies have examined emissions from High stearate fuels with few double bonds produce signifi-
biodiesel and studies through 1997 have been cantly less NOx than certification diesel. On the basis of
reviewed.[68,69] Studies employing heavy-duty transient this evidence, we conclude that shorter chain esters produce
testing generally show that emissions of PM and CO are higher NOx emissions, but note that the fully saturated
reduced and NOx emissions are increased relative to pet- methyl laurate still produced NOx at or below the certifi-
roleum diesel. PM can be viewed as being made of cation fuel level. Therefore, shortening of the hydrocarbon
carbon or soot, a soluble organic fraction (SOF) and sul- chain may be a route to NOx neutral fuels with improved
fate. Graboski and coworkers[69] tested methyl soyester properties. While NOx emissions increase with increasing
and diesel-soy ester blends in a 1991 Detroit Diesel Series density or iodine number, or decreasing cetane number,
60 (four-stroke) engine. For 35% biodiesel, the composite PM emissions remain unchanged. NOx emissions formed
NOx emission increased by nearly 1%, while the composite in an engine are highly dependent on combustion tempera-
particulate emission decreased by 26% relative to the refer- ture, along with the concentration of oxygen present in
ence diesel. For 100% biodiesel, the composite NOx combustion products. NOx emissions from biodiesel are
increased by 11% while PM was decreased by 66%. More generally slightly higher than those from no. 2 diesel.[71]
recent studies have shown similar levels of PM reduction Biodiesels rich oxygen content is also a factor in high
and NOx increase.[70] The system for emissions measure- NOx formation levels. Szybist et al. suggested the use of
ment for regulated pollutants (THC, CO, NOx, and PM) cetane improving additives and modified feedstock compo-
is identical to that described by McCormick and sition to reduce NOx emission from biodiesel fueled diesel
coworkers.[68] All components and procedures meet the engines.[72] The higher NOx emissions are mainly because
BIOFUELS 423

the biodiesel blend has a shorter ignition delay time. One used in many engines built with little or no modification.
of the most effective ways to reduce NOx emission is to Transportation and storage, however, require special man-
lower the temperature inside the engine cylinder using agement. Material compatibility and warranty issues have
water injection, water emulsified biodiesel, ignition timing not been resolved with higher blends. Using biodiesel in a
retardation, or exhaust gas recirculation.[73] conventional diesel engine substantially reduces emissions
From an operational point of view, biodiesel has about of unburned hydrocarbons, carbon monoxide, sulfates,
90% of the energy content of petroleum diesel, measured polycyclic aromatic hydrocarbons, nitrated polycyclic aro-
on a volumetric basis. Due to this fact, on average the matic hydrocarbons, and particulate matter. These reduc-
use of biodiesel reduces the fuel economy and power of tions increase as the amount of biodiesel blended into
an engine by about 10% in comparison with petroleum die- diesel fuel increases. In general, biodiesel increases NOx
sel. The reason for this reduction stems mainly from the emissions when used as fuel in diesel engines. This could
oxygen content of biodiesel, the ensuing better combustion be solved by using system of dual injection. Here, a small
process, and improved lubricity, which partly compensate amount of diesel is injected as a pilot fuel for the ignition
for the impact of the lower energy content. Biodiesel is source. A large amount of alcohol is injected as the main
an oxygenated compound. Oxygenates are just preused fuel. It must be noted that the pilot fuel must be injected
hydrocarbons having a structure that provides a reasonable prior to injection of alcohol. Some ideal results can be
antiknock value. Also, as oxygenates contain oxygen; fuel achieved when this method is used. The thermal efficiency
combustion is more efficient, reducing hydrocarbons in is better. At the same time, NOx emissions are lower.
exhaust gases. The only disadvantage is that oxygenated Moreover, CO emissions and HC emissions are the same.
fuel has less energy content. On the other hand, biodiesel However, the system requires two fuel pumps, thus result-
blends are safer than pure petroleum diesel because biodie- ing in a high cost. In general, biodiesel will soften and
sel has a higher flash point. The most common blend is a degrade certain types of elastomers and natural rubber
mix of 20% biodiesel with 80% petroleum diesel, or B20 compounds over time.
in recent scientific investigations; however, in Europe the
current regulation foresees a maximum 5.75% biodiesel.
Most operational disadvantages of pure biodiesel, for CONCLUSIONS
example, replacement of natural rubber seals, cold start The direct use of vegetable oils and=or oil blends is
problems, etc., do not arise with blended kinds of biodiesel. generally considered to be unsatisfactory and impractical for
Fuel characterization data show some similarities and both direct injection and indirect type diesel engines because
differences between biodiesel fuels and diesel:[74] of their high viscosities and low volatilities injector coking
and trumpet formation on the injectors, higher level of carbon
. Specific weight is higher for biodiesel, heat of
deposits, oil ring sticking, and thickening and gelling of
combustion is lower, and viscosities are 1.3 to
the engine lubricant oil, acid composition. Consequently,
1.6 times that of D2 fuel.
. Pour points for biodiesel fuels vary from 274 to
different methods have been considered to reduce the viscosity
of vegetable oils such as dilution, microemulsification, pyrol-
298 K higher for biodiesel fuels depending on
ysis, catalytic cracking, and transesterification. Biodiesel as it
the feedstock.
is defined today is obtained by transesterifying triglycerides
. Sulfur content for biodiesel fuel is 20 to 50% that
with methanol. Methanol is the preferred alcohol for obtain-
of D2 fuel.
ing biodiesel because it is the cheapest alcohol. Base catalysts
. Methyl esters have higher levels of injector coking
are more effective than acid catalysts and enzymes.
than D2 fuel.
A popular variation of the batch transesterification
The methyl ester of vegetable oil was evaluated as a fuel process which needs high alcohol=acid ratio (several separ-
in compression ignition engines (CIEs).[41,75] The authors ation problems and high corrosivity and toxicity) is the use
concluded that the performance of the esters of vegetable of continuous stirred tank reactors in series. Instead of
oil did not differ greatly from that of diesel fuel. The brake allowing time for the reaction in an agitated tank, the reac-
power of biodiesel was nearly the same as with diesel fuel, tor is tubular. This continuous process is heterogeneous
while the specific fuel consumption was higher than that of and is based on reactive distillation. Easy separation and
D2. Based on crankcase oil analysis, engine wear rates were environmental friendly process belong to main advantages
low, but some oil dilution did occur. Carbon deposits of whole process. The key factor is the selection of the right
inside the engine were normal, with the exception of intake and effective solid catalyst which leads to reduction of
valve deposits. Blends of up to 20% biodiesel mixed with energy consumption and investments at all.
petroleum diesel fuels can be used in nearly all diesel A novel processes of biodiesel fuel production have been
equipment and are compatible with most storage and developed by a noncatalytic supercritical methanol method
distribution equipment. Higher blends, even B100, can be which involves simpler purification, has a lower reaction
424 I. KRALOVA AND J. SJÖBLOM

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