Documente Academic
Documente Profesional
Documente Cultură
25
Keywords: Alternative fuels, biodiesel, transesterification, FAEEs, FAMEs, lipase, SCF, refinery, NOx, microdiesel.
INTRODUCTION
The biggest challenge modern industrial society is facing today
is the decline and exhaustion of the fossil energy resources. The
primary sources of energy that power our civilization are those
fossil fuels. The International Energy Agency has forecasted that
the world's total energy requirements will rise by half in the next 25
years. On the other hand, global oil product demand has been
revised to 84.3 million barrels a day (mb/d) in 2006 and 85.8 mb/d
in 2007 [1]. Therefore continued use of petroleum-sourced fuels is
now widely recognized as unsustainable because of depleting
supplies and increasing demand.
Oil prices have been rising steadily over the past 3 years and
surged to a record high above $60 a barrel in June 2005, sustaining
a rally built on strong demand for gasoline and diesel and on
concerns about refiners' ability to keep up. This trend continued
into early August 2005, as NYMEX crude oil futures contracts
surged past the $65 mark as consumers kept up the demand for
gasoline despite its high price. Crude oil futures peaked at a close of
over $78.40 per barrel on July 13, 2006 [2].
In addition, the combustion of the fossil fuels used is
considered as the major factor responsible for global warming due
to large-scale carbon dioxide emissions. The present atmospheric
concentration of CO2 is about 383 parts per million (ppm) by
volume. Future CO2 levels are expected to rise due to ongoing
burning of these fossil fuels and land-use change. The IPCC Special
Report on Emissions Scenarios gives a wide range of future CO 2
scenarios, ranging from 541 to 970 ppm by the year 2100. Fossil
fuel reserves are sufficient to reach this level and continue
emissions past 2100, if coal, tar sands or methane clathrates are
extensively used [3]. Fossil fuels are also considered as the main
source of local environmental pollution. Thus, alternative energy
sources based on sustainable, renewable and environmentally
friendly processes are urgently needed. One of the most prominent
alternative energy resources, attracting more and more interest in
recent years with the price for crude oil reaching record heights, is
biodiesel, which is a possible substitute for petroleum-based diesel
fuel. Biodiesel fuels are the alkyl monoesters of fatty acids from
vegetable oils and animal fats. Many studies have shown that the
properties of biodiesel are very close to diesel fuel [4-6]. Therefore,
*Address correspondence to this author at the Group of Environmental
Microbiology, Institute of Water Research, University of Granada,
C/Ramn y Cajal No. 4, Edificio Fray Luis de Granada, Granada 18071,
Spain; Tel: +34 958 242981; Fax: +34 958 243094;
E-mail: manzanera@ugr.es
1872-2083/08 $100.00+.00
Manzanera et al.
Biodiesel
insoluble solids from the liquid by injecting gas bubbles into the
wastewater solution. These bubbles adhere to the insoluble particles
and form a floating layer of sludge, which is mechanically scraped
off producing an emulsion of fat and protein in water in significant
quantities whose disposal is both problematic and expensive. The
method by Hamilton RB involves adjustment of the DAF sludge pH
between 2.5 and 4.5, mixing it with an emulsifying agent and
heating the mixture to boiling point. By allowing the mixture to
cool down the fat and protein component parts separate out, and fat
rich component is then used as biodiesel feedstock [40].
2. METHODS FOR BIODIESEL PRODUCTION
Biodiesel production is mainly performed by the transesterification of a triglyceride with an alcohol in a chemical reaction
known as alcoholysis outlined in Fig. (1). In the transesterification
of different types of oils, triglycerides react with an alcohol,
generally methanol or ethanol, to produce esters and glycerol. The
overall process is normally a sequence of three consecutive
reversible reactions [41,42]. During the first reaction, triglycerides
are transformed into diglycerides. Then from diglycerides,
monoglycerides are produced in the second reaction and in the last
reaction glycerol is obtained from monoglycerides. In all these
reactions esters are produced which are the products used as
biodiesel, that finally as the resulting product has to be purified.
The stechiometric relation between alcohol and oil is 3:1. However,
an excess of alcohol is usually added to improve the reaction
towards the desired product. To make the reaction possible, a
catalyst is added as well. This transesterification reaction is affected
by alcohol type, molar ratio of alcohol to oil, temperature, purity of
the reactants and type and amount of catalyst see [43] for a review.
Different types of catalysts are used, from basic ones such as
sodium or potassium hydroxides, acids such as sulfuric acid, ion
exchange resins, lipases and supercritical fluids. For a basic
catalyst, either sodium hydroxide (NaOH) or potassium hydroxide
(KOH) is normally used with methanol or ethanol as well as any
kind of oils, although sodium and potassium alkoxides such as
sodium methoxide, sodium ethoxide, sodium propoxide, sodium
butoxideto have been proposed as alkali catalysts as well. In this
process it is better to produce the alcoxide before the reaction to
obtain a better global efficiency [44]. The alcohol-oil molar ratio
that should be used varies from 1:1-6:1. However, 6:1 is the most
used ratio giving an important conversion for the alkali catalyst
without using a great amount of alcohol. The types of alcohol are
usually methanol and ethanol. The last one has fewer safety
problems because it is less toxic, but methanol is most frequently
used because of its lower cost and its physical and chemical
advantages (polar and shortest chain alcohol), although in some
countries such as Brazil, there is a special interest in developing an
appropriate technology for the use of ethanol instead of methanol
[45] since ethanol is easily available due to the extensive
fermentation industry in the country.
27
Manzanera et al.
Biodiesel
29
Table 1.
Manzanera et al.
Comparison of the Different Technologies to Produce Biodiesel (from Marchetti et al., [96])
Variable
Alkali catalysis
Lipase catalysis
Supercritical
Acid catalysis
Alcohol.
Reaction temperature (oC)
60-70
30-40
239-385
55-80
Saponified products
Methyl esters
Esters
Esters
No influence
Normal
Higher
Recovery of glycerol
Difficult
Easy
Difficult
Repeated washing
None
Repeated washing
Cheap
Relatively expensive
Medium
Normal
Cheap
Biodiesel
31
4. AVOIDING DRAWBACKS
4.1. NOx (Nitrogen Oxide) Emissions
If biodiesel improves engine emissions in most categories when
compared to petroleum based diesel fuel, however it is also
responsible for an increase in nitrous oxide emissions. Blends
containing higher concentrations of biodiesel, show a proportional
increase in emissions of nitrogen oxides (NOx). Presently, NOx
emissions could be a significant limitation to the widespread
adoption of biodiesel fuels. NOx is a generic term for mononitrogen oxides. These oxides are produced during combustion, and
are of interest as air pollution. They are believed to aggravate
breathing conditions, to produce ozone at surface heights, which is
also an irritant, and to react with the oxygen present in the air, and
eventually can form nitric acid when dissolved in water [130].
When NOx is dissolved in atmospheric moisture it can result in acid
rain that potentially can damage entire forests. Some researchers
have sought to address the NOx issue by the addition of certain fuel
additives to the biodiesel. For example, Bradin described a fuel
additive composition including fatty acid alkyl esters and glyceryl
ethers. The additive-containing fuel is made by a multi-step process
that includes separation of glycerol from biodiesel, conversion of
glycerol to glycerol ether, and then addition of the glycerol ether
back into the biodiesel fuel [52]. Other researchers describe
controlling engine emission NOx by producing a blending of a
synthetic middle distillate derived from Fischer-Tropsch produced
synthesis gas (syngas) and biodiesel, which generate very low
levels of NOx and sulfur emissions when used in diesel engines
[131]. Addition of water to the fuel, to cool down the combustion
process reduces the formation of NOx as well. However, that
process undesirably lowers fuel BTU (British Thermal Units) value
by replacing fuel with water. A large number of materials have
been found to be catalytically active for selective catalytic reduction
of NOx. By far, the most widely reported in the open literature are
metal-exchanged zeolites, such as Cu-ZSM-5, Co-ZSM-5, and FeZSM-5. However, the zeolite-based materials lose much of their
activity when water (common in exhaust streams) is added to the
exhaust stream. While other catalysts that possess greater water
stability have been found, such as metal-supported oxides, these
tend to lack the desired activity shown by the metal zeolites, and
produce large amounts of N2O (also a major pollutant). Baacke et
al. described a zeolite catalyst and a method for reduction of
nitrogen oxides by mixing the waste gas with ammonia [132].
However, the use of ammonia in the reduction of nitrogen oxide is
less desirable, especially in transportation systems, due to the toxic
nature of the ammonia that must be stored locally, presenting a
hazard.
On the other hand, Green et al. described a single phase catalyst
obtained by intimately mixing the powders of the oxide binder and
the metal salts. This patent describes the mixing of particles of a
metal exchanged zeolite with an oxide [133,134]. Also Sachtler and
Chen described that the metal can be introduced into the zeolite in
an entirely different way, such as by metal vapor deposition [135].
Recently advances in the use of cerium-oxide, have been described
to hold the potential to nearly eliminate NOx emissions from both
petrodiesel and biodiesel, and diesel fuel additives based on cerium
oxide that can improve fuel consumption by 11% in unmodified
diesel engines [136]. Recently, a catalyst for reducing nitrogen
oxide has been developed to remove NOx and particulate matter
using platinum as activating element [137].
4.3. Oxidation Stability
A different problem in using biodiesel is that since biodiesel has
a higher content of unsaturated fatty acid esters, it easily oxidizes in
the presence of oxygen, UV light, heat, or trace metals, such as iron
or copper. The products formed from this oxidation give rise to
sediment and gum formation within the fuel and lead to corrosion
Manzanera et al.
petroleum-based diesel. However, different and combined protocols, apparatus and feedstock would be needed in order to produce
biodiesel in large quantities.
The most promising alternatives in order to obtain an
environmentally friendly product are based on technology with
biological origin especially those methods catalyzed by lipases.
This technology works at the lowest reaction temperature; it is not
influenced by the presence of water or free fatty acid in the
feedstock, hence reducing the production cost, and produces the
highest yields of biodiesel. In addition, the lipase technology allows
an easy recovery of glycerol, without the need of purifying the
methyl esters. It is of paramount importance to reduce the
production cost derived from the protein purification though.
Therefore, the use of whole microorganisms, as biodiesel cell
factories, with the ability to synthesize alcohol esters could save
this enzyme purification cost.
Steinbchel and coworkers have created a fuel-refining
Escherichia coli bacterial strain by modifying it with genes taken
from two other microorganisms, Zymomonas mobilis and
Acinetobacter baylyi [143]. The modified E. coli were cultured in
growth medium containing glucose and oleic acid, which the
bacteria processed into fatty acid ethyl esters, a diesel-substitute
named as "microdiesel". This was achieved by heterologous
expression in E. coli of the Zymomonas mobilis pyruvate
decarboxylase and alcohol dehydrogenase and the unspecific
acyltransferase from Acinetobacter baylyi strain ADP1. By this
approach Steinbchel et al., managed to obtain ethanol formation
and to combine it with a subsequent esterification of the ethanol
with the acyl moieties of coenzyme A thioesters of fatty acids.
Using this transgenic microorganism the obtained concentration of
FAEE was of 1.28 g/L and the FAEE content of the cells was of 26
% of the cellular dry mass, that were achieved by fed-batch
fermentation using renewable carbon sources.
This novel approach might pave the way for industrial
production of biodiesel equivalents from renewable resources by
employing engineered microorganisms, enabling a broader use of
biodiesel-like fuels in the future.
Unlike regular biofuel, microdiesel is produced without toxic
chemicals. Waste oils could allegedly be used as source of fatty
acids, reducing the need to grow crops specifically for biodiesel
production and therefore reducing the production cost of this fuel.
ABBREVIATIONS
IEA
=
International energy agency
NYMEX
=
New York mercantile exchange
IPCC
=
Intergovernmental panel on climate change
NREL
=
US National renewable energy laboratory
FAMEs
=
Fatty acid methyl esters
FAEEs
=
Fatty acid ethyl esters
DAF
=
Dissolved air flotation
SCF
=
Super critical fluid
BTU
=
British termal units
ACKNOWLEDGEMENTS
Maximino Manzanera was granted by Programa Ramn y Cajal
(MEC, Spain and ERDF, Euopean Union).
REFERENCES
[1]
[2]
[3]
[4]
International Energy Agency. Oil Market Report. A monthly oil market and
stocks assessment. 13 March 2007. http://omrpublic.iea.org/
http://www.nymex.com
IPCC WGI Fourth Assessment Report. Intergovernmental panel on climate
change. February, 2007.
Mittelbach M, Pokits B, Silberholz A. Production and fuel properties of fatty
acid methyl esters from used frying oil. In: Liquid fuels from renewable
Biodiesel
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
33
Vieira, J.A., Sabba, M., Dias-Bruna, S., Ferreira, C., De Menezes, S.:
WO07020465 (2007).
Wright HJ, Segur JB, Clark HV, Coburn SK, Langdon EE, DuPuis RN. A
report on ester interchange. Oil and Soap 1944; 21: 145-148.
Freedman B, Pryde EH, Mounts TL. Variables affecting the yields of fatty
esters from transesterified vegetable oils. JAOCS 1984; 61: 1638-1643.
Stern, R., Hillion, G., Gateau, P., Guibet, J.C.: US4695411 (1984).
Skopal, F., Komers, K., Machek, J., Koropecky, I.: CZ20050155 (2006).
Kraft, P., Gilbeau, P., Gosselin, B., Claessens, S.: EP1770081 (2007).
Jakobson, G., Siemanowski, W.: US4960953 (1990).
Bradin, D.S.: US5578090 (1996).
Gupta, V.P.: US5476971 (1995).
Kesling, Jr H.S., Karas, L.J., Liotta, Jr J.: US5308365 (1994).
Noureddini, H.: US20006015440 (2000).
Bradin, D.S.: WO07027669 (2007).
Srivastava A, Prasad R. Triglycerides-based diesel fuels. Renew Sust Energy
Rev 2000; 4:111-33.
Wimmer, T.: US5399731 (1995).
Harrington KJ, Darcy-Evans C. Trans-esterification insitu of sunflower seed
oil. Ind Eng Chem Prod Res Dev 1985; 24:314.
Stern R, Perdu O, Hillion G. Replacement gas oils from vegetable oil esters:
an opportunity for some countries. Revue del Institut Francais du Petrole.
1988; 43: 883-893.
Zhang Y, Dube MA, McLean DD, Kates M. Biodiesel production from
waste cooking oil: 1. Process design and technological assessment.
Bioresource Technol 2003; 89: 1-16.
Aksoy HA, Kahraman I, Karaosmanoglu F, Civelekoglu H. Evaluation of
turkish sulfur olive oil as an alternative diesel fuel. JAOCS 1988; 65: 936-8.
Kawahara, Y.; Ono, T.: US4164506 (1979).
Jeromin, L., Peukert, E., Wollmann, G.: US4698186 (1987).
Tanaka, Y., Okabe, A., Ando, S.: US4303590 (1981).
Basu, H.N., Norris, M.E.: US5525126 (1996).
Gupta, A.K., Bhatnagar, A.K., Kaul S.: WO05063954 (2005).
Portnoff, M.A., Purta, D.A., Nasta, M.A., Pourarian, F., Zhang, J.:
EP1765762 (2007).
Nelson LA, Fogolia TA, Marmer WN. Lipase-catalyzed production of
biodiesel. J Am Oil Chem Soc 1996; 73: 1191.
Kaieda M, Samukawa T, Kondo A, Fukuda H. Effect of methanol and water
contents on production of biodiesel fuel from plant oil catalyzed by various
lipases in a solvent-free system. J Biosci Bioeng 2001; 91: 12-15.
Kose O, Tuter M, Aksoy HA. Immobilized Candida antarctica lipasecatalyzed alcoholysis of cotton seed oil in a solvent-free medium. Bioresour
Technol 2002; 83: 125-129.
Wu WH, Foglia TA, Marmer WN, Phillips JG. Optimizing production of
ethyl esters of grease using 95% ethanol by response surface methodology. J
Am Oil Chem Soc 1999; 76:517-521.
Abigor RD, Uadia PO, Foglia TA, et al. Lipase-catalysed production of
biodiesel fuel from some Nigerian lauric oils. Biochem Soc Trans 2000;
28:979-981.
Belafi-Bako K, Kovacs F, Gubicza L, Hancsok J. Enzymatic biodiesel
production from sunflower oil by candida antarctica lipase in a solvent-free
system. Biocat Biotransf 2002; 20:437-439.
Shieh CJ, Liao HF, Lee CC. Optimization of lipase-catalyzed biodiesel by
response surface methodology. Bioresour Technol 2003; 88:103-106.
Fukuda, H., Otsuka K., Nomoto, F.: US2000270886 (2000).
Foglia, T.A., Nelson, L.A., Marmer, W.N.: US5713965 (1998).
Hsu AF, Jones K, Foglia TA, Marmer WN. Immobilized lipase-catalysed
production of alkyl esters of restaurant grease as biodiesel. Biotechnol Appl
Biochem 2002; 36:181-186.
Shimada Y, Watanabe Y, Samukawa T, et al. Conversion of vegetable oil to
biodiesel using immobilized Candida antarctica lipase. J Am Oil Chem Soc
1999; 76:789-793.
Iso M, Chen BX, Eguchi M, Kudo T, Shreestha S. Production of biodiesel
fuel from triglycerides and alcohol using immobilized lipase. J Mol Catal B
Enzymatic 2001; 16:53-58.
Wu, W.T., Chen, J.W.: US20026398707 (2002).
Wu, W.T., Chen, J.W.: DE10217607 (2002).
Wu, W.T., Chen, J.W.: TW491890B (2002).
Sato, S., Bueno, A.W., Shigueu, A.A.: WO06050589 (2006).
Liu, H., Ma, Y., Xue, Y.: CN1611600 (2005).
Fukuda, H., Noda H.: US20066982155 (2006).
Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in
supercritical methanol. Fuel 2001; 80: 225-231;
Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to
biodiesel fuel as treated in supercritical methanol. Fuel 2001; 80: 693-693.
[99]
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[107]
[108]
[109]
[110]
[111]
Manzanera et al.
[112]
[113]
[114]
[115]
[116]
[117]
[118]
[119]
[120]
[121]
[122]
[123]
[124]
[125]
[126]
[127]
[128]
[129]
[130]
[131]
[132]
[133]
[134]
[135]
[136]
[137]
[138]
[139]
[140]
[141]
[142]
[143]