Demirbas (2005

Progress in Energy and Combustion Science 31 (2005) 466487 www.elsevier.
com/locate/pecs
Biodiesel production from vegetable oils via catalytic and non-catalytic supercritical methanol transesterication methods
Ayhan Demirbas *
Department of Chemical Engineering, Selcuk University, Campus, 42031 Konya, Turkey Received 18 April 2005; accepted 23 September 2005
Abstract This paper reviews the production and characterization of biodiesel (BD or B) as well as the experimental work carried out by many researchers in this eld. BD fuel is a renewable substitute fuel for petroleum diesel or petrodiesel (PD) fuel made from vegetable or animal fats. BD fuel can be used in any mixture with PD fuel as it has very similar characteristics but it has lower exhaust emissions. BD fuel has better properties than that of PD fuel such as renewable, biodegradable, non-toxic, and essentially free of sulfur and aromatics. There are more than 350 oil bearing crops identied, among which only sunower, safower, soybean, cottonseed, rapeseed and peanut oils are considered as potential alternative fuels for diesel engines. The major problem associated with the use of pure vegetable oils as fuels, for Diesel engines are caused by high fuel viscosity in compression ignition. Dilution, micro-emulsication, pyrolysis and transesterication are the four techniques applied to solve the problems encountered with the high fuel viscosity. Dilution of oils with solvents and microemulsions of vegetable oils lowers the viscosity, some engine performance problems still exist. The viscosity values of vegetable oils vary between 27.2 and 53.6 mm2/s whereas those of vegetable oil methyl esters between 3.59 and 4.63 mm2/s. The viscosity values of vegetable oil methyl esters highly decreases after transesterication process. Compared to no. 2 diesel fuel, all of the vegetable oil methyl esters were slightly viscous. The ash point values of vegetable oil methyl esters are highly 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. The purpose of the transesterication process is to lower the viscosity of the oil. The transestercation of triglycerides by methanol, ethanol, propanol and butanol, has proved to be the most promising process. Methanol is the commonly used alcohol in this process, due in part to its low cost. Methyl esters of vegetable oils have several outstanding advantages among other newrenewable and clean engine fuel alternatives. The most important variables affecting the methyl ester yield during the transesterication reaction are molar ratio of alcohol to vegetable oil and reaction temperature. Biodiesel has become more attractive recently because of its environmental benets. Biodiesel is an environmentally friendly fuel that can be used in any diesel engine without modication. q 2005 Elsevier Ltd. All rights reserved.
Keywords: Alternative fuel; Vegetable oil; Biodiesel; Viscosity; Transesterication; Methanol
Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467 468
* Tel.: C90 462 230 7831; fax: C90 462 248 8508. E-mail address: 8508.ayhandemirbas@hotmail.com
0360-1285/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.pecs.2005.09.001
A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487
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2.
3.
4.
5. 6. 7.
1.2. The use of vegetable oils and their derivatives as alternative diesel fuels . . . . . . . . . . . . . . . . . . . . . . . . . 1.3. Global vegetable oil resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Biodiesel (BD) as an alternative fuel for diesel engine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. The importance of alcohols for diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Methanol production methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2. Ethanol production methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Hydrogen production methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Transesterication of vegetable oils and fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Catalytic transesterication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Supercritical methanol transesterication method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Recovery of glycerol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4. Reaction mechanism of transesterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.1. Acid-catalyzed processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.2. Alkali-catalyzed processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.3. Enzyme-catalyzed processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.4. Non-catalytic supercritical alcohol transesterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fuel properties of vegetable oils and biodiesels (BDs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Emissions from biodiesel combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Comparison of fuel properties and combustion characteristics of methyl and ethyl alcohols and their esters Engine performance tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . BD economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
468 469 470 471 471 472 473 474 474 475 477 477 478 478 479 479 479 482 482 483 483 484 484
1. Introduction The major part of all energy consumed worldwide comes from fossil sources (petroleum, coal and natural gas). However, these sources are limited, and will be exhausted by the near future. Thus, looking for alternative sources of new and renewable energy such as hydro, biomass, wind, solar, geothermal, hydrogen and nuclear is of vital importance. Alternative new and renewable fuels have the potential to solve many of the current social problems and concerns, from air pollution and global warming to other environmental improvements and sustainability issues [1]. Vegetable oil is one of the renewable fuels. Vegetable oils have become more attractive recently because of its environmental benets and the fact that it is made from renewable resources. Vegetable oils are a renewable and potentially inexhaustible source of energy with an energetic content close to diesel fuel. The vegetable oil fuels were not acceptable because they were more expensive than petroleum fuels. However, with recent increases in petroleum prices and uncertainties concerning petroleum availability, there is renewed interest in vegetable oil fuels for diesel engines [2]. Diesel boiling range material is of particular interest because it has been shown to signicantly reduce
particulate emissions relative to petroleum diesel [3]. There are more than 350 oil-bearing crops identied, among which only sunower, safower, soybean, cottonseed, rapeseed, and peanut oils are considered as potential alternative fuels for diesel engines [4,5]. The major problem associated with the use of pure vegetable oils as fuels, for diesel engines are caused by high fuel viscosity in compression ignition. The use of vegetable oils as alternative renewable fuel competing with petroleum was proposed in the beginning of 1980s. The advantages of vegetable oils as diesel fuel are [2]: Liquid nature-portability Ready availability Renewability Higher heat content (about 88% of no. 2 diesel fuel) Lower sulfur content Lower aromatic content Biodegradability The disadvantages of vegetable oils as diesel fuel are: Higher viscosity Lower volatility The reactivity of unsaturated hydrocarbon chains
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1.1. History Transesterication of triglycerides are in oils is not a new process. Scientists E. Duffy and J. Patrick conducted it as early as 1853. Life for the diesel engine began in 1893 when the famous German inventor Rudolph Diesel published a paper entitled The theory and construction of a rational heat engine. What the paper described was a revolutionary engine in which air would be compressed by a piston to a very high pressure thereby causing a high temperature. Rudolph Diesel designed the original diesel engine to run on vegetable oil. Dr Rudolph Diesel used peanut oil to fuel one of this his engines at the Paris Exposition of 1900 [6]. Because of the high temperatures created, the engine was able to run a variety of vegetable oils including hemp and peanut oil. At the 1911 Worlds Fair in Paris, Dr R. Diesel ran his engine on peanut oil and declared the diesel engine can be fed with vegetable oils and will help considerably in the development of the agriculture of the countries which use it. One of the rst uses of transesteried vegetable oil was powering heavy-duty vehicles in South Africa before world war II. The name biodiesel has been given to transesteried vegetable oil to describe its use as a diesel fuel [7]. 1.2. The use of vegetable oils and their derivatives as alternative diesel fuels The direct use of vegetable oils in fuel engines is problematic. Due to their high viscosity (about 1117 times higher than diesel fuel) and low volatility, they do not burn completely and form deposits in the fuel injector of diesel engines [2]. Different ways have been considered to reduce the high viscosity of vegetable oils: (1) Dilution of 25 parts of vegetable oil with 75 parts of diesel fuel, (2) Microemulsions with short chain alcohols such as ethanol or methanol, (3) Thermal decomposition, which produces alkanes, alkenes, carboxylic acids and aromatic compounds, (4) Catalytic cracking, which produces alkanes, cycloalkanes and alkylbenzenes, and (5) Transesterication with ethanol or methanol. Dilution of oils with solvents and microemulsions of vegetable oils lowers the viscosity, some engine performance problems, such as injector coking and more carbon deposits. still exist Among all these
alternatives, the transesterication seems to be the best choice, as the physical characteristics of fatty acid esters (biodiesel) are very close to those of diesel fuel and the process is relatively simple. Furthermore, the methyl or ethyl esters of fatty acids can be burned directly in unmodied diesel engines, with very low deposit formation. Although short-term tests using neat vegetable oil showed promising results, longer tests led to injector coking, more engine deposits, ring sticking, and thickening of the engine lubricant. These experiences led to the use of modied vegetable oil as a fuel. Although there are many ways and procedures to convert vegetable oil into a diesel-like fuel, transesterication process was found to be the most viable oil modication process [8]. At present, the most common way to produce biodiesel (BD or B) is to transesterify triacylglycerols in vegetable oil or animal fats with an alcohol in the presence of an alkali or acid catalyst. BD is a renewable substitute fuel for petroleum diesel (PD) made from vegetable or animal fats via transesterication by alcohols. BD can be used in any mixture with PD as it has very similar characteristics but it has lower exhaust emissions. BD has better properties than that of PD such as renewable, biodegradable, non-toxic, and essentially free of sulfur and aromatics. Chemically, BD is referred to as the mono-alkylesters of long-chain-fatty acids derived from renewable lipid sources. BD is the name for a variety of ester based oxygenated fuel from renewable biological sources. It can be used in compression ignition engines with little or no modications [9]. A number of methods exist to blend vegetable oil with PD and create a low viscosity fuel oil with similar properties to diesel. Benets are substantially reduced engine emissions, even with as small a blend as 20% BD with 80% PD. Using BD results in large reductions in overall carbon dioxide emissions and it is carbon dioxide that is a major contributor to climate change. Exploring new energy resources, such as BD fuel, is of growing importance in recent years. BD is recommended for use as a substitute for PD mainly because BD is a renewable, domestic resource with an environmentally friendly emission prole and is readily available and biodegradable [10]. BD has become more attractive recently because of its environmental benets [11,12]. This paper reviews the production and characterization of BD from vegetable oils as well as the experimental work carried out by many researchers in this eld. Several types of vegetable oils can be used for the preparation of BD. Soybean, rapeseed, sunower
A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487 Table 1 Fatty acid compositions of vegetable oil samples Sample Cottonseed Poppyseed Rapeseed Safowerseed Sunowerseed Sesameseed Linseed Wheat graina Palm Corn marrow Castorb Tallow Soybean Bay laurel leafc Peanut kerneld Hazelnut kernel Walnut kernel Almond kernel Olive kernel Coconute 16:0 28.7 12.6 3.5 7.3 6.4 13.1 5.1 20.6 42.6 11.8 1.1 23.3 13.9 25.9 11.4 4.9 7.2 6.5 5.0 7.8 16:1 0 0.1 0 0 0.1 0 0.3 1.0 0.3 0 0 0.1 0.3 0.3 0 0.2 0.2 0.5 0.3 0.1 18:0 0.9 4.0 0.9 1.9 2.9 3.9 2.5 1.1 4.4 2.0 3.1 19.3 2.1 3.1 2.4 2.6 1.9 1.4 1.6 3.0 18:1 13.0 22.3 64.1 13.6 17.7 52.8 18.9 16.6 40.5 24.8 4.9 42.4 23.2 10.8 48.3 83.6 18.5 70.7 74.7 4.4 18:2 57.4 60.2 22.3 77.2 72.9 30.2 18.1 56.0 10.1 61.3 1.3 2.9 56.2 11.3 32.0 8.5 56.0 20.0 17.6 0.8 18:3 0 0.5 8.2 0 0 0 55.1 2.9 0.2 0 0 0.9 4.3 17.6 0.9 0.2 16.2 0 0 0 Others 0 0 0 0 0 0 0 1.8 1.1 0.3 89.6 2.9 0 31.0 4.0 0 0 0.9 0.8 65.7
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Legend: Source: Ref. [2]. a Wheat grain oil contains 11.4% of 8:0 and 0.4% of 14:0 fatty acids. b Castor oil contains 89.6% ricinoloic acid. c Bay laurel oil contains 26.5% of 12:0 and 4.5% of 14:0 fatty acids. d Peanut kernel oil contains about 2.7% of 22:0 and 1.3% of 24:0 fatty acids. e Coconut oil contains about 8.9% of 8:0, 6.2% 10:0, 48.8% of 12:0 and 19.9% of 14:0 fatty acids.
and palm oils are the most studied. However, there are no technical restrictions to the use of other types of vegetable oils. The fatty acid compositions of vegetable oil samples are given in Table 1. Considering the type of the alcohol, the use of methanol is advantageous as it allows the simultaneous separation of glycerol. The same reaction using ethanol is more complicated as it requires a water-free alcohol, as well as an oil with a low water content, in order to obtain glycerol separation [13]. Problems met in long-term engine tests according to results obtained by earlier researchers may be classied as follows: Injector coking and trumpet formation on the injectors, more carbon deposits, oil ring sticking, and thickening and gelling of the engine lubricant oil [2]. The vegetable oils were all extremely viscous with viscosities ranging 1020 times greater than no. 2 diesel fuel. Castor oil is in a class by itself with a viscosity more than 100 times that of no. 2 diesel fuel [2]. Viscosity of oil can be lowered by blending with pure ethanol. 25 parts of sunower oil and 75 parts of PD were blending as PD fuel. Dilution, micro-emulsication, pyrolysis and transesterication are the four techniques applied to solve the problems encountered
with the high fuel viscosity. To reduce of the high viscosity of vegetable oils, microemulsions with immiscible liquids such as methanol and ethanol and ionic or non-ionic amphiphiles have been studied [12,14]. Vegetable oils have the potential to substitute a fraction of petroleum distillates and petroleum based petrochemicals in the near future. Vegetable oil fuels are not petroleum-competitive fuels because they are more expensive than petroleum fuels. 1.3. Global vegetable oil resources Global vegetable oil production increased 56 million tons in 1990 to 88 million tons in 2000, following a below-normal increase. World vegetable and marine oil consumption is tabulated in Table 2. Fig. 1 shows the plots of percentages the world oil consumption by years. Fig. 2 shows the total global production and consumption of vegetable oil by years. Leading the gains in vegetable oil production was a recovery in world palm oil output, from 17.1 million tons in 1997/1998 to 19.3 million in 1998/1999. The major exporters of vegetable oils are Malaysia, Argentina, Indonesia, Philippines, and Brazil.
470

90000
Table 2 World vegetable and marine oil consumption (million metric ton) Oil Soybean Palm Rapeseed Sunowerseed Peanut Cottonseed Coconut Palm kernel Olive Fish Total 1998 23.5 18.5 12.5 9.2 4.5 3.7 3.2 2.3 2.2 1.2 80.7 1999 24.5 21.2 13.3 9.5 4.3 3.7 3.2 2.6 2.4 1.2 85.7 2000 26.0 23.5 13.1 8.6 4.2 3.6 3.3 2.7 2.5 1.2 88.4 2001 26.6 24.8 12.8 8.4 4.7 4.0 3.5 3.1 2.6 1.3 91.8 2002 27.2 26.3 12.5 8.2 5.3 4.4 3.7 3.5 2.7 1.3 95.1 2003 27.9 27.8 12.1 8.0 5.8 4.9 3.9 3.7 2.8 1.4 98.3
Total production Amount of vegetable oil, Million ton
Total consumption
80000
70000
60000
Source: World statistics, 19982004 United Soybean Board.
The major importers of vegetable oils are China, Pakistan, Italy and the United Kingdom. Few countries such as Netherlands, Germany, United States and Singapore are both large exporters as well as importers of vegetable oils [8]. Global vegetable oil exports rose modestly from 29.8 million tons in 1997/1998 to 31.2 million in 1998/1999. A large portion of the gain went to India, where even small price shifts can cause a substantial change in consumption. Indian consumption of all vegetable oils in 1998/1999 soared 26% from 1997/1998. Indian palm oil imports climbed to a record 2.5 million tons. Similarly, Pakistan, Iran, Egypt, and Bangladesh sharply increased their vegetable oil imports. In 1999, Pakistan reacted to falling vegetable oil prices with a series of increases that doubled the import duties on soybean oil and palm oil, while eliminating duties on oilseeds. Pakistan also raised the import duty on soybean meal from 10 to 35% to stem the inux of Indian exports [8].
Soybean Palm Rapeseed Sunflowerseed Peanut Others
50000 1990
1992
1994
1996
1998
2000
Years
Fig. 2. Total global production and consumption of vegetable oil by years.
2. Biodiesel (BD) as an alternative fuel for diesel engine BD is a clear amber-yellow liquid with a viscosity similar to PD. BD is non-ammable, and in contrast to PD it is non-explosive, with a ash point of 423 K for BD as compared to 337 K for PD. Unlike PD, BD is biodegradable and non-toxic, and it signicantly reduces toxic and other emissions when burned as a fuel. Currently, BD is more expensive to produce than PD, which appears to be the primary factor keeping it from being in more widespread use. Current worldwide production of vegetable oil and animal fat is not enough to replace liquid fossil fuel use (maximum replacement percentage: w2025%) [8]. Methyl esters of vegetable oils (BDs) have several outstanding advantages among other new-renewable and clean engine fuel alternatives. Methanol as monoalcohol is generally used in the transesterication reaction of triglycerides in the presence alkali as a catalyst [15]. Methanol is a relatively inexpensive alcohol. Several common vegetable oils such as sunower, palm, rapeseed, soybean, cottonseed and corn oils and their fatty acids can be used as the sample of vegetable oil. BD is easier to produce and cleaner with equivalent amounts of processing when starting with clean vegetable oil. The tallow, lard and yellow grease BDs need additional processing at the end of transesterication due to including high free fatty acid. Diesel derived from rapeseed oil is the most common
Annual oil consumption, wt%
28
22
16
10
4 1998
1999
2000 Year
2001
2002
2003
Fig. 1. Plots of percentages the world oil consumption by years. Source: World Statistics, 19982004 United Soybean Board.
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BD available in Europe, while soybean BD is dominant in the United States. The emergence of the transesterication can be dated back to as early as 1846 when Rochieder described glycerol preparation through ethanolysis of castor oil [16]. Since, that time alcoholysis has been studied in many parts of the world. Others researchers have also investigated the important reaction conditions and parameters on the alcoholysis of triglycerides, such as sh oils, tallow, soybean, rapeseed, cottonseed, sunower, safower, peanut and linseed oils [1726]. It also prepared methyl esters from palm oil by transesterication using methanol in the presence of a alkali catalyst in a batch reactor [27]. Soybean oil was transesteried into ethyl and methyl esters, and compared the performances of the fuels with PD [28,29]. Transesterication is the process of using an alcohol (e.g. methanol, ethanol, propanol or butanol), in the presence of a catalyst to chemically break the molecule of the raw renewable oil into methyl or ethyl esters of the renewable oil with glycerol as a by-product [2]. Methanol is the commonly used alcohol in this process, due in part to its low cost. However, ethanol is a preferred alcohol in the transesterication process compared to methanol because it is derived from agricultural products and is renewable and biologically less objectionable in the environment. Alkali catalyzed transesterication has been most frequently used industrially, mainly due to its fast reaction rate. Methyl, ethyl, 2-propyl and butyl esters were prepared from canola and linseed oils through transesterication using KOH and/or sodium alkoxides as catalysts. In addition, methyl and ethyl esters were prepared from rapeseed and sunower oils using the same catalysts [22]. 2.1. The importance of alcohols for diesel engines Practically, any of the organic molecules of the alcohol family can be used as a fuel. The alcohols that can be used for motor fuels are methanol (CH3OH), ethanol (C2H5OH), propanol (C 3H7OH), butanol (C4H9OH). However, only two of these alcohols (methanol and ethanol) are technically and economically suitable as fuels for internal combustion engines (ICEs). Main production facilities of methanol and ethanol are tabulated in Table 3. Methanol is produced by a variety of process, the most common are as follows: Distillation of liquid products from wood and coal, natural gas and petroleum gas. Ethanol is produced mainly from biomass bioconversion. It can
Table 3 Main production facilities of methanol and ethanol Product Methanol Distillation of liquid from wood pyrolysis Gaseous products from biomass gasication Distillation of liquid from coal pyrolysis Synthetic gas from biomass and coal Natural gas Petroleum gas Ethanol Fermentation of sugars and starches Bioconversion of cellulosic biomass Hydration of alkanes Synthesis from petroleum Synthesis from coal Enzymatic conversion of synthetic gas Production process
also be produced by synthesis from petroleum or mineral coal [30]. 2.1.1. Methanol production methods Methanol, also known as wood alcohol, is commonly used in BD production for its reactivity. Generally, it is easier to nd than ethanol. Sustainable methods of methanol production are currently not economically viable. The use of methanol as a motor fuel received attention during the oil crises of the 1970s due to its availability and low cost. Problems occurred early in the development of gasolinemethanol blends. As a result of its low price some gasoline marketers over blended. Many tests have shown promising results using 85100% by volume methanol as a transportation fuel in automobiles, trucks and buses [8]. Methanol can be used as one possible replacement for conventional motor fuels. Methanol has been seen as a possible large volume motor fuel substitute at various times during gasoline shortages. It was often used in the early part of the century to power automobiles before inexpensive gasoline was widely introduced. In the early 1920s, some viewed it as a source of fuel before new techniques were developed to discover and extract oil. Synthetically produced methanol was widely used as a motor fuel in Germany during the world war. Before modern production technologies were developed in the 1920s, methanol was obtained from wood as a co-product of charcoal production and, for this reason, was commonly known as wood alcohol. Methanol is currently manufactured worldwide by conversion or derived from syngas, natural gas, renery off-gas, coal or petroleum:
472
2H2 C CO/ CH3 OH
(1)
The chemical composition of syngas from coal and then from natural gas can be identical with the same H2/CO ratio. A variety of catalysts are capably of causing the conversion, including reduced NiO-based preparations, reduced Cu/ZnO shift preparations, Cu/SiO2 and Pd/SiO2, and Pd/ZnO [31,32]. Biomass resources can be used to produce methanol. The pyroligneous acid obtained from wood pyrolysis consists of about 50% methanol, acetone, phenols and water. [33,34]. As a renewable resource, biomass represents a potentially inexhaustible supply of feedstock for methanol production. The product yield for the conversion process is estimated to be 185 kg of methanol per metric ton of solid waste [35,36]. Methanol is currently made from natural gas but can be made using wood waste or garbage via partial oxidation reaction into syngas, followed by catalytic conversion into methanol called as biomethanol. Adding sufcient hydrogen to the syngas to convert all of the biomass carbon into methanol carbon would more than double the methanol produced from the same biomass base [37]. The composition of syngas from biomass for producing methanol is presented in Table 4. Current natural gas feedstocks are so inexpensive that even with tax incentives renewable methanol has not been able to compete economically. Technologies are being developed that may eventually result in commercial viability of renewable methanol. Methanol from coal could be a very important source of liquid fuel in the future. The coal is rst pulverized and cleaned, then fed to a gasier bed where it is reacted with oxygen and steam to produce the syngas. Once these steps have been taken, the production process is much the same as with the other feedstocks with some variations in the catalyst used and the design of the converter vessel in which the reaction is carried out. Methanol made using synthesis gas (syngas) with hydrogen and carbon monoxide in a 21 ratio (Table 4). The syngas was transformed to methanol in a xed catalyst bed reactor. Coal-derived methanol has many preferable properties as free of sulfur and other impurities, could replace petroleum in transportation, or be used as a peaking fuel in combustion turbines, or supply a source of hydrogen
Table 4 Analysis of syngas from typical coal Gases Percentage CO 45.3 H2 34.4 CO2 15.8 CH4 1.9 N2 1.9 Ar 0.6
for fuel cells. The technology for making methanol from natural gas is already in place and requires only efciency improvements and scale-up to make methanol an economically viable alternative transportation fuel. In recent years, a growing interest has been observed in the application of methanol as an alternative liquid fuel, which can be used directly for powering Otto engines or fuel cells [38]. Biomass and coal can be considered as a potential fuel for gasication and further syngas production and methanol synthesis [32, 33]. The feasibility of achieving the conversion has been demonstrated in a large scale system in which a product gas is initially produced by pyrolysis and gasication of a carbonaceous matter. Syngas from biomass is altered by catalyst under high pressure and temperature to form methanol. This method will produce 100 gallons of methanol per ton of feed material [38] Table 5. 2.1.2. Ethanol production methods Ethanol, also known as grain alcohol, not commonly used in making BD because of its low reactivity than methanol. Ethanol is an alcohol-based fuel produced by fermenting sugars from crop starches. Currently, ethanol is generally produced from corn kernels in USA. In this process, kernels are ground to a ne powder, and all of it is cooked to liquefy it, without removing the germ or ber. Ethanol has been used in Germany and France as early as 1894 by the then incipient industry of ICEs. Brazil has utilized ethanol as a fuel since 1925. Currently, ethanol is produced from sugar beets and from molasses in Brazil. A typical yield is 72.5 liter of ethanol per ton of sugar cane. Modern crops yield 60 ton of sugar cane per hector of land. Production of ethanol from biomass is one way to reduce both the consumption of crude oil and environmental pollution [39]. The use of gasohol (ethanol and gasoline mixture) as an alternative motor fuel has been steadily increasing in the world for a number of reasons. Domestic production and use of ethanol for fuel can decrease dependence on foreign oil, reduce trade decits, create
Table 5 Composition of syngas from biomass for producing methanol (% by volume) H2 3241 CO 2129 CH4 1015 CO2 1419 C2H4 0.81.2 H2 O 5.56.5 N2 0.61.2
Source: Ref. [30].
Source: Ref. [7].
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jobs in rural areas, reduce air pollution, and reduce global climate change carbon dioxide buildup [40]. 2.2. Hydrogen production methods Hydrogen can be produced by several methods. The predominant method for producing syngas is steam reforming of natural gas, although other hydrocarbons can be used as feedstocks. Approximately 95% of the hydrogen is produced from fossil fuels conversion, such as natural gas reforming. Steam reforming of natural gas is an endothermic, catalytic process carried out at about 1125 K and around 2.5 MPa according to the following reactions: CH4 C H2 O / CO C 3H2 CO C H2 O / CO2 C H2 (2) (3)
Table 6 List of some biomass material used for hydrogen production Biomass species Bio-nut shell Olive husk Tea waste Crop straw Black liquor Municipal solid waste Crop grain residue Pulp and paper waste Petroleum basis plastic waste Manure slurry Main conversion process Steam gasication Pyrolysis Pyrolysis Pyrolysis Steam gasication Supercritical water extraction Supercritical uid extraction Microbiol fermentation Supercritical uid extraction Microbiol fermentation
Syngas or articial water gas (COCH2) from coal can be reformed to hydrogen. Hydrogen and oxygen concentrations in coal increase as coal rank goes down. The water vapor (steam) can be further shifted to hydrogen by establishing conditions to drive the reaction to produce additional hydrogen: Coal C H2 O / CO C H2 (4)
Near-term production of renewable hydrogen from biomass requires a co-product strategy to compete with conventional production of hydrogen from the steam reforming of natural gas. The processing of pyrolysis co-products from the production of activated carbon is one possible path to demonstrate such a strategy. Renewable hydrogen has the potential of being cost effective and is environmentally friendly. The production of renewable hydrogen from biomass as a renewable resource requires a co-product strategy to compete with conventional production of hydrogen from the steam reforming of natural gas. The process of biomass to activated carbon is an alternative route to hydrogen with a valuable co-product that is practiced commercially [41]. Currently Czernik et al. [42] have developed a method for producing hydrogen from biomass and concluded that a co-products strategy could compete with the cost of the commercial natural gas-based technologies [43,44]. The yield of hydrogen that can be produced from biomass is relatively low, 1618% based on dry biomass weight [45]. Only the carbohydrate-derived bio-oil fraction produced from biomass undergoes reforming. The strategy is based on producing hydrogen from biomass pyrolysis using a coproduct strategy to reduce the cost of hydrogen. The process of biomass to activated carbon is an alternative
route to hydrogen with a valuable co-product that is practiced commercially. The list of some biomass material used for hydrogen production is given in Table 6. The rst intermediate temperatures between 600 and 850 K pyrolysis carries out through the formation mainly acetic acid, which partly forms H2, CO2 and CO and a small amount of methane. The second intermediate temperatures between 900 and 1100 K pyrolysis carries out through the formation mainly propionic acid, which partly forms H2, CO2 and CO and a small amount of ethylene, which partly reacts with hydrogen to form ethane [46]. The high temperature pyrolysis carries out via the formation of unstable free radicals which react with water to form H2 and CO2 in approximately a molar ratio of 2 mol of H2 per mol of CO2 formed. The gas products of H2, CO2, CO, CH4 and C2H6 are formed by the secondary pyrolytic gasication reactions, they will continue to react according to two reversible tertiary reactions. The rst is the water-gas shift reaction [43]: CO C H2 O $ CO2 C H2 and the second is the CH4 formation reaction: CO C 3H2 O $ CH4 C H2 O (6) (5)
Hydrogen can be produced from biomass via two thermochemical processes: (a) gasication followed by reforming of the syngas, and (b) fast pyrolysis followed by reforming of the carbohydrate fraction of the bio-oil. In each process, water-gas shift is used to convert the reformed gas into hydrogen, and pressure swing adsorption is used to purify the product. Comparison with other biomass thermochemical gasication such as air gasication and/or steam gasication, the supercritical water gasication can directly deal with the wet biomass without drying, and have high gasication efciency in lower temperature. The cost of hydrogen
474
Supercritical fluid extraction

Conventional pyrolysis Steam gasification
50 45 40 35 30 25 20 15 10 600
700
800
900 1000 Temperature, K
1100
1200
Fig. 3. Plots for yield of hydrogen from supercritical uid (water) extraction, pyrolysis and steam gasication [(W/S)Z2] of beech wood at different temperatures. Source: Ref. [48].
production from supercritical water gasication of wet biomass was several times higher than the current price of hydrogen from steam methane reforming. Biomass was gasied in supercritical water at a series of temperature and pressure during different resident times to form a product gas composed of H2, CO2, CO, CH4, and a small amount of C2H4 and C2H6 [47]. Fig. 3 shows the curves for yield of hydrogen from supercritical uid extraction (SFE), pyrolysis and steam gasication [(W/S)Z2] of beech wood at different temperatures. Distilled water was used in the SFE (the critical temperature of pure water is 647.7 K). As seen from Fig. 3, the yield of hydrogen from SFE was considerably high (49%) at lower temperatures. The pyrolysis was carried out at the moderate temperatures and steam gasication at the highest temperatures [48]. The oily liquid fraction from pyrolysis consisted of two phases: an aqueous phase containing a wide variety of organo-oxygen compounds of low molecular weight and a non-aqueous tarry phase containing insoluble organics of high molecular weight. Tar a viscous black uid that is a byproduct of the pyrolysis of woody biomass. The chief constituents of tar are pyrocatechol, phenol, guaiacol, cresol, creosol, methyl-creosol, phlorol, toluene, xylene, naphthalene, and other hydrocarbons.
3. Transesterication of vegetable oils and fats The transesterication reaction proceeds with catalyst or without any catalyst by using primary or secondary monohydric aliphatic alcohols having 18 carbon atoms as follows: Triglycerides C Monohydric alcohol % Glycerin C Mono- alkyl esters (7)
Transesterication means taking a triglyceride molecule or a complex fatty acid, neutralizing the free fatty acids, removing the glycerin, and creating an alcohol ester. The reaction is shown in Eq. (7). Theoretically, transesterication reaction is an equilibrium reaction. In this reaction, however, more amount of methanol was used to shift the reaction equilibrium to the right side and produce more methyl esters as the proposed product. A catalyst is usually used to improve the reaction rate and yield. Alcohols are primary or secondary monohydric aliphatic alcohols having 18 carbon atoms Amongs the alcohols that can be used in the transesterication reaction are methanol, ethanol, propanol, butanol and amyl alcohol. Methanol and ethanol are used most frequently, ethanol is a preferred alcohol in the transesterication process compared to methanol because it is derived from agricultural products and is renewable and biologically less objectionable in the environment. However methanol is preferable because of its low cost and its physical and chemical advantages (polar and shortest chain alcohol). The transesterication reaction can be catalyzed by alkalis [10,49], acids [50], or enzymes [5155]. Several alcoholysis catalysts, known to be effective for reactions between simple alcohols and soybean oil, were evaluated and found to be ineffective toward alcoholysis of ethylene glycol with soybean oil under traditional reaction conditions. An initial survey of alternative catalysts revealed that organometallic tin complexes were effective but unsatisfactory due to toxicity and difculty in recovering the catalyst. Satisfactory performance for several alcoholysis reactions was achieved with calcium carbonate catalysts even though at higher temperatures, typically greater than 475 K [56]. The physical properties of the primary chemical products of transesterication are given in Tables 7 and 8 [11,57,58]. In the conventional transesterication of animal fats and vegetable oils for biodiesel production, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which resulting in a low conversion [59]. 3.1. Catalytic transesterication method The catalyst is dissolved into methanol by vigorous stirring in a small reactor. The oil is transferred into the BD reactor and then the catalyst/alcohol mixture is
Yield of hydrogen, vol.%
A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487 Table 7 Physical properties of chemicals related to transesterication Name Specic gravity (g/ml) 0.875 0.825 0.850 0.875 0.792 0.789 1.260 Melting point (K) 291.0 303.8 311.2 253.4 176.2 161.2 255.3 Boiling point (K) 469.2 488.2 463.2 337.9 351.6 563.2 Solubility (!10%) Benzene, EtOH, Et2O Et2O, chloroform EtOH, Et2O H2O, ether, EtOH H2O, ether H2O, ether Table 9 Critical temperatures and critical pressures of various alcohols Alcohol Methanol Ethanol 1-Propanol 1-Butanol Critical temperature (K) 512.2 516.2 537.2 560.2 Critical pressure (MPa) 8.1 6.4 5.1 4.9
475
Methyl myristate Methyl palmitate Methyl stearate Methyl oleate Methanol Ethanol Glycerol
3.2. Supercritical methanol transesterication method [7] The transestercation of triglycerides by supercritical methanol (SCM), ethanol, propanol and butanol, has proved to be the most promising process. Table 9 shows critical temperatures and critical pressures of various alcohols. A non-catalytic BD production route with supercritical methanol has been developed that allows a simple process and high yield because of simultaneous transesterication of triglycerides and methyl esterication of fatty acids [9]. Because of having similar properties to PD, BD, a transesteried product of vegetable oil, is considered as the most promising one for diesel fuel substitute. A reaction mechanism of vegetable oil in SCM was proposed based on the mechanism developed by Krammer and Vogel [60] for the hydrolysis of esters in sub/supercritical water. The basic idea of supercritical treatment is a relationship between pressure and temperature upon thermophysical properties of the solvent such as dielectric constant, viscosity, specic weight, and polarity [61]. The transesterication of sunower oil was investigated in SCM and supercritical ethanol at various temperatures (475675 K) [62]. Fig. 4 shows a SCM transesterication system. The most important variables affecting the methyl ester yield during transesterication reaction are molar
Source: Refs. [7,57].
pumped into the oil. The nal mixture is stirred vigorously for 2 h at 340 K in ambient pressure. A successful transesterication reaction produces two liquid phases: ester and crude glycerol. Crude glycerol, the heavier liquid, is collected at the bottom after several hours of settling. Phase separation can be observed within 10 min and can be complete within 2 h of settling. Complete settling can take as long as 20 h. After settling is complete, water is added at the rate of 5.5% by volume of methyl ester of oil and then stirred for 5 min and the glycerin is allowed to settle again. Washing the ester is a two-step process, which is carried out with extreme care. A water wash solution at the rate of 28% by volume of oil and g of tannic acid/liter of water is added to the ester and gently agitated. Air is carefully introduced into the aqueous layer while simultaneously stirring very gently. This process is continued until the ester layer becomes clear. After settling, the aqueous solution is drained and water alone is added at 28% by volume of oil for the nal washing [2,7,11].
Table 8 Melting points of fatty acids, methyl esters and mono-, di-, and triglycerides (K) Name Myristic Palmitic Stearic Oleic Linoleic Fatty acid 327.6 292.0 343.7 340.0 330.2 Methyl ester 336.1 303.8 350.2 349.5 336.7 1-Monoglyceride 342.8 312.3 254.7 352.6 346.3 1,3-Diglyceride 289.5 253.4 308.4 294.7 278.7 Triglyceride 266.7 238.2 285.5 270.6 260.1
Source: Refs. [7,58].
Fig. 4. Supercritical methanol transesterication system. (1) Autoclave; (2) electrical furnace; (3) temperature control monitor; (4) pressure control monitor; (5) product exit valve; (6) condenser; (7) product collecting vessel. Source: Ref. [2].
476
100

100
Yield of methyl ester, wt%
Yield of methyl ester, wt%
90 80 70 60 50 40 30 20 10 0
1.0:1.0 1.0:3.0 1.0:9.0 1.0:20 1.0:41
80
60 450 K 493 K 503 K 20 513 K 523 K 0 0 50 100 150 200 250 300 350
40
50
50
150
250
350
Reaction time (sec)

Fig. 5. Changes in yield percentage of methyl esters as treated with subcritical and supercritical methanol at different temperatures as a function of reaction time. Molar ratio of vegetable oil to methyl alcohol: 1:41. Sample: hazelnut kernel oil. Source: Ref. [7].
Reaction time (sec)

Fig. 6. Effect of molar ratio of vegetable oil to methanol on yield of methyl ester. Temperature: 513 K, sample: methylester from cottonseed oil. Source: Ref. [7].
ratio of alcohol to vegetable oil and reaction temperature. Viscosities of the methyl esters from the vegetable oils were slightly higher than that of no. 2 diesel fuel. Fig. 5 shows a typical example of the relationship between the reaction time and the temperature [7]. The variables affecting the ester yield during transesterication reaction are molar ratio of alcohol to vegetable oil, reaction temperature, reaction time, water content and catalyst. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable inuence on ester conversion [7]. In the transesterication process, the vegetable oil should have an acid value less than one and all materials should be substantially anhydrous. If the acid value is greater than one, more NaOH or KOH is injected to neutralize the free fatty acids. Water can cause soap formation and frothing. The resulting soaps can induce an increase in viscosity, formation of gels and foams, and made the separation of glycerol difcult [11,63]. The stoichiometric ratio for transesterication reaction requires 3 mol of alcohol and 1 mol of triglyceride to yield 3 mol of fatty acid ester and 1 mol of glycerol. Higher molar ratios result in greater ester production in a shorter time. The vegetable oils are transesteried 1:61:40 vegetable oil-alcohol molar ratios in catalytic and supercritical alcohol conditions [7]. Fig. 6 shows the effect of the molar ratio of vegetable oil to methanol on the yield of methyl ester.
As seen in Fig. 6, the cottonseed oil can be transesteried at 1:1, 1:3, 1:9, 1:20 and 1:40 vegetable oil-methanol molar ratios in subcritical and SCM conditions [7]. In the supercritical alcohol transesterication method, the yield of conversion raises 5095% for the rst 10 min. Fig. 7 shows the plots for changes in fatty acids alkyl esters conversion from triglycerides as treated in supercritical alcohols at 575 K [64]. Water content is an important factor in the conventional catalytic transesterication of vegetable oil. In the conventional transesterication of fats and vegetable oils for BD production, free fatty acids and water always produce negative effects since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. However, the presence of water affected positively the formation of methyl esters in our SCM method. Fig. 7 shows the plots for yields of methyl esters as a function of free fatty acid content in BD production [64]. Transesterication reaction of rapeseed oil in SCM has been investigated without using any catalyst. In addition, it was found that this new SCM process requires the shorter reaction time and simpler purication procedure because of the unused catalyst [2,7]. Transesterication can occur at different temperatures and the temperature inuence the reaction rate and yield of esters, depending on the oil used. It was observed that increasing reaction

100
477
Fatty acid alkyl ester, %
80
60 Methanol 40 Ethanol 1-Propanol 20 1-Butanol 1-Octanol
10
20 30 Reaction time, min
40
50
ester transesterication occurs. This is accomplished by mixing methanol with sodium hydroxide to make sodium methoxide. This dangerous liquid is then mixed into vegetable oil. Washing the methyl ester is a two step process which is carried out with extreme care.. This procedure is continued until the methyl ester layer becomes clear. After settling, the aqueous solution is drained and water alone is added at 28% by volume of oil for the nal washing. The resulting BD fuel when used directly in a diesel engine will burn up to 75% cleaner than no. 2 PD fuel [8]. 3.4. Reaction mechanism of transesterication Transesterication consists of a number of consecutive, reversible reactions [65,66]. The triglyceride is converted stepwise to diglyceride, monoglyceride and nally glycerol (Eqs. 811). The formation of alkyl esters from monoglycerides is believed as a step which determines the reaction rate, since monoglycerides are the most stable intermediate compound [11]. Fatty acid R1 COOH C Alcohol ROH $ Ester R1 COOR C Water H2 O Triglyceride C ROH $ Diglyceride C RCOOR1 Diglyceride C ROH $ Monoglyceride C RCOOR2 Monoglyceride C ROH $ Glycerol C RCOOR3 (11) (10) (8) (9)
Fig. 7. Plots for changes in fatty acids alkyl esters conversion from triglycerides as treated in supercritical alcohol at 575 K. Source: Ref. [64].
temperature, especially supercritical temperatures had a favorable inuence on ester conversion [7]. 3.3. Recovery of glycerol The standards make sure that the following important factors in the BD fuel production process by transesterication are satised: (a) complete transesterication reaction, (b) removal of catalyst, (c) removal of alcohol, (d) removal of glycerol, and (e) complete esterication of free fatty acids. The following transesterication procedure is for the methyl ester production. The catalyst is dissolved into the alcohol by vigerous stirring in a small reactor. The oil is transferred into the BD reactor and then the catalyst/methanol mixture is pumped into the oil and nal mixture stirred vigorously for 2 h. A successful reaction produces two liquid phases: ester and crude glycerol. The entire mixture then settles and glycerol is left on the bottom and methyl esters (BD) is left on top. Crude glycerol, the heavier liquid will collect at the bottom after several hours of settling. Phase separation can be observed within 10 min and can be complete within 2 h after stirring has stopped. Complete settling can be taken as long as 18 h. After settling is complete, water was added at the rate of 5.0% by volume of the oil and then stirred for 5 min and the glycerol allowed settling again. After settling is complete the glycerol is drained and the ester layer remains [8]. The recovery of high quality glycerol as a BD byproduct is primary options to be considered to lower the cost of BD. With neutralizing the free fatty acids, removing the glycerol, and creating an alcohol
Several aspects, including the type of catalyst (alkaline, acid or enzyme), alcohol/vegetable oil molar ratio, temperature, water content and free fatty acid content have an inuence on the course of the transesterication. In the transesterication of vegetable oils and fats for biodiesel production, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which result in a low conversion [67]. When the original ester is reacted with an alcohol, the transesterication process is called alcoholysis [68]. The transesterication is an equilibrium reaction and the transformation occurs essentially by mixing the reactants.
478
In the transesterication of vegetable oils, a triglyceride reacts with an alcohol in the presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol. The stoichiometric reaction requires 1 mol of a triglyceride and 3 mol of the alcohol. However, an excess of the alcohol is used to increase the yields of the alkyl esters and to allow its phase separation from the glycerol formed [8]. 3.4.1. Acid-catalyzed processes The transesterication process is catalyzed by acids, preferably by sulfonic and sulfuric acids. These catalysts give very high yields in alkyl esters, but the reactions are slow. The alcohol/vegetable oil molar ratio is one of the main factors that inuence the transesterication. An excess of alcohol favors the formation of the products. On the other hand, an excessive amount of alcohol makes the recovery of the glycerol difcult, so that the ideal alcohol/oil ratio has to be established empirically, considering each individual process. The protonation of the carbonyl group of the ester leads to the carbocation which, after a nucleophilic attack of the alcohol, produces the tetrahedral intermediate, which eliminates glycerol to form the new ester, and to regenerate the catalyst HC. According to this mechanism, carboxylic acids can be formed by reaction of the carbocation with water present in the reaction mixture and acid-catalyzed transesterication should be carried out in the absence of water [8,68]. Acid catalytic transesterication of
vegetable oils were carried out in several studies [50, 69]. Solid superacid catalysts of sulfated tin and zirconium oxides and tungstated zirconia were used in the transesterication of soybean oil with methanol at 475575 K and the esterication of n-octanoic acid with methanol at 450475 K. Tungstated zirconia alumina is a promising catalyst for the production of biodiesel fuels because of its activity for the transesterication as well as the esterication [69]. 3.4.2. Alkali-catalyzed processes The reaction mechanism for alkali-catalyzed transesterication was formulated as three steps [70,71]. The alkali-catalyzed transesterication of vegetable oils proceeds faster than the acid-catalyzed reaction. The mechanism of the base-catalyzed transesterication of vegetable oils is shown in Fig. 8. The rst step is the reaction of the base with the alcohol, producing an alkoxide and the protonated catalyst. The nucleophilic attack of the alkoxide at the carbonyl group of the triglyceride generates a tetrahedral intermediate, from which the alkyl ester and the corresponding anion of the diglyceride are formed. The latter deprotonates the catalyst can react with a second molecule of alcohol and starts another catalytic cycle. Diglycerides and monoglycerides are converted by the same mechanism to a mixture of alkyl esters and glycerol. Alkaline metal alkoxides (CH3ONa) are the most active catalysts, since they give very high yields (O98%) in short reaction times (30 min) even if they are applied at low molar concentrations (0.5 mol%). The presence of water gives
Fig. 8. Mechanism of the alkali-catalyzed transesterication of vegetable oils (B: base).
479
Acid catalyst
Methyl ester, %
rise to hydrolysis of some of the produced ester, with consequent soap formation. Potassium carbonate, used in a concentration of 2 or 3 mol% gives high yields of fatty acid alkyl esters and reduces the soap formation. This can be explained by the formation of bicarbonate instead of water (Fig. 8), which does not hydrolyse the esters [8,68]. 3.4.3. Enzyme-catalyzed processes Although the enzyme-catalyzed transesterication processes are not yet commercially developed, new results have been reported in a recent article [68]. The common aspects of these studies consist in optimizing the reaction conditions (solvent, temperature, pH, type of microorganism which generates the enzyme, etc) in order to establish suitable characteristics for an industrial application. However, the reaction yields as well as the reaction times are still unfavorable compared to the base-catalyzed reaction systems [8]. 3.4.4. Non-catalytic supercritical alcohol transesterication BD, an alternative diesel fuel, is made from renewable biological sources such as vegetable oils and animal fats by non-catalytic supercritical alcohol transesterication methods [2]. A non-catalytic BD production route with supercritical methanol has been developed that allows a simple process and high yield because of simultaneous transesterication of triglycerides and methyl esterication of fatty acids [7]. The parameters affecting the methyl esters formation are reaction temperature, pressure, molar ratio, water content and free fatty acid content. It is evident that at subcritical state of alcohol, reaction rate is very low and gradually increases as either pressure or temperature rises. It was observed that increasing the reaction temperature, especially to supercritical conditions, had a favorable inuence on the yield of ester conversion [2,7]. The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol [6]. In the supercritical alcohol transesterication method, the yield of conversion raises 5095% for the rst 10 min. Water content is an important factor in the conventional catalytic transesterication of vegetable oil. In the conventional transesterication of fats and vegetable oils for biodiesel production, free fatty acids and water always produce negative effects since the presence of free fatty acids and water causes soap formation consumes catalyst and reduces catalyst effectiveness. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. However, the presence of water affected
Supercritical methanol
Alkaline catalyst
100 80 60 40 20 0 0 1 2 3 4 5 Water content, %
Fig. 9. Plots for yields of methyl esters as a function of water content in transesterication of triglycerides.
positively the formation of methyl esters in our supercritical methanol method. Fig. 9 shows the plots for yields of methyl esters as a function of water content in transesterication of triglycerides. Fig. 10 shows the plots for yields of methyl esters as a function of free fatty acid content in BD production [67]. Comparisons between catalytic commercial methanol process and supercritical methanol (SCM) method for BD from vegetable oils by transesterication are given in Table 10. 4. Fuel properties of vegetable oils and biodiesels (BDs) Vegetable oils can be used as fuel for combustion engines, but its viscosity is much higher than usual diesel fuel and requires modications of the engines. The major problem associated with the use of pure vegetable oils as fuels, for diesel engines are caused by high fuel viscosity in compression ignition. Therefore, vegetable oils are converted into their methyl esters (BDs) by transesterication. Viscosity is a measure of the internal friction or resistance of an oil to ow. As the temperature of oil is
Supercritical methanol alkaline catalyst Acid catalyst
100 Methyl ester, % 80 60 40 20 0 0 10 20 Free fatty acid content, % 30
Fig. 10. Plots for yields of methyl esters as a function of free fatty acid content.
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A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487 Table 12 Viscosity, density and ash point measurements of 10 vegetable oils Oil source Viscosity (mm2/s (at 311 K)) 34.9 33.5 53.6 27.2 39.6 37.0 31.3 35.5 32.6 33.9 Density (kg/m3) 909.5 914.8 904.4 923.6 902.6 911.5 914.4 913.3 913.8 916.1 Flash point (K) 550 509 447 514 544 519 533 533 527 447
Table 10 Comparisons between catalytic methanol (MeOH) process and supercritical methanol (SCM) method for biodiesel from vegetable oils by transesterication Catalytic MeOH process Methylating agent Catalyst Reaction temperature (K) Reaction pressure (MPa) Reaction time (min) Methyl ester yield (wt%) Removal for purication Free fatty acids Methanol Alkali 303338 0.1 60360 96 Methanol, catalyst, glycerol, soaps Saponied products SCM method Methanol None 523573 1025 715 98 Methanol Methyl esters, water
Corn Cottonseed Crambe Linseed Peanut Rapeseed Safower Sesame Soybean Sunower
The biodiesel (BD) was characterized by determining its density, viscosity, high heating value, cetane number, cloud and pour points, characteristics of distillation, and ash and combustion points according to ISO norms. Source: Ref. [4].
increased, its viscosity decreases and it is therefore able to ow more readily. Viscosity is measured on several different scales, including Redwood no. 1 at 100F, Engler Degrees, Saybolt Seconds, etc. Viscosity is the most important property of biodiesel since it affects the operation of fuel injection equipment, particularly at low temperatures when the increase in viscosity affects the uidity of the fuel. BD has viscosity close to diesel fuels. High viscosity leads to poorer atomization of the fuel spray and less accurate operation of the fuel injectors. A novel process of BD fuel production has been developed by a non-catalytic supercritical methanol method. Viscosity, density and ash point measurements of eight oil methyl esters are given in Table 11. Compared to no. 2 diesel fuel, all of the vegetable oils were much more viscous. Viscosity, density and ash point measurements of ten vegetable oils given by Goering et al. [4] are shown in Table 11. The density values of vegetable oils are between 902.6 and 923.6 kg/m3 while
Table 11 Viscosity, density and ash point measurements of eight oil methyl esters Methyl ester Viscosity (mm2/s (at 313 K)) 3.69 3.59 4.10 3.70 4.63 4.03 4.08 4.22 Density (kg/m3 (at 288 K)) 880 860 881 870 885 880 885 880 Flash point (K) 437 401 446 443 428 453 447 443
Cottonseed oil Hazelnut kernel oil Mustard oil Palm oil Rapeseed oil Safower oil Soybean oil Sunower oil Source: Ref. [72].
those of vegetable oil methyl esters are between 860 and 885 kg/m3 (Table 12). The density values of vegetable oil methyl esters considerably decreases via transesterication process. The viscosity values of vegetable oils are between 27.2 and 53.6 mm2/s whereas those of vegetable oil methyl esters are between 3.59 and 4.63 mm2/s. The viscosity values of vegetable oil methyl esters highly decreases after transesterication process. Compared to no. 2 PD fuel, all of the vegetable oil methyl esters were slightly viscous. The ash point values of vegetable oil methyl esters are highly lower than those of vegetable oils (Tables 11 and 12). Density is another important property of BD. It is the weight of a unit volume of uid. Specic gravity is the ratio of the density of a liquid to the density of water. Specic gravity of BD fuels ranges between 0.87 and 0.89 kg/m3 (Table 11). Fuel injection equipment operates on a volume metering system, hence a higher density for BD results in the delivery of a slightly greater mass of fuel. Cetane number (CN) is a measure of ignition quality of diesel fuel. The higher the CN, the easier the fuel ignites when it is injected into the engine. The higher the CN is the more fuel-efcient the fuel. BD has a higher CN than petrol diesel because of its higher oxygen content. This means that engines run smoother and create less noise when running on BD. The CN is based on two compounds, namely hexadecane with a CN of 100 and heptamethylnonane with a CN of 15. The CN scale also shows that straight-chain, saturated hydrocarbons have higher CN compared to branchedchain or aromatic compounds of similar molecular weight and number of carbon atoms. The CN of
481
biodiesel is generally higher than conventional PD. The CN is one of the prime indicators of the quality of diesel fuel. It relates to the ignition delay time of a fuel upon injection into the combustion chamber. The CN is a measure of ignition quality of diesel fuels and high CN implies short ignition delay. The longer the fatty acid carbon chains and the more saturated the molecules, the higher the CN. The CN of BD from animal fats is higher than those of vegetable oils. Comparisons of some fuel properties of vegetable oils and their esters with diesel fuel are given in Table 13. Table 14 shows some fuel properties of six methyl ester BDs given in literature. Relationships between density and viscosity of vegetable oils are depicted in Fig. 11. These gures were plotted using the values in Table 12 given by Goering et al. [4]. As seen Fig. 11, an increase in density from 902.6 to 923.6 kg/m3 for vegetable oils decreases the viscosity from 53.6 to 27.2 mm2/s and the decreases are considerably regular (coefcient of regression (r) is 0.7942). Relationships between density and viscosity of vegetable oil methyl esters are depicted in Fig. 12. The Fig. 12 was plotted using the measured values [72]. As seen Fig. 12, an increase in density from 860 to 885 kg/m3 for vegetable oil methyl esters or BDs increases the viscosity from 3.59 to 4.63 mm2/s. There is high regression between density and viscosity values vegetable oil methyl esters. The relationships between viscosity and ash point for vegetable oil methyl esters are irregular.
Table 13 Comparisons of some fuel properties of vegetable oils and their esters with diesel fuel Fuel type Caloric value (MJ/kg) 43.4 39.5 40.6 39.6 40.6 39.6 39.8 37.8 38.9 37.6 Density (kg/m3) 815 918 878 912 874 914 872 915 921 914 Viscosity at 300 K (mm2 /s) 4.3 58.5 10.3 50.1 11.1 65.4 11.1 46.3 56.1 39.2 Cetane numbera 47.0 37.1 45.5
Table 14 Fuel properties of methyl ester biodiesels Source Viscosity (g/mL at 288.7 K) 4.6 4.1 5.7 4.9 3.6 4.1 Density (cSt at 313. 2 K) 0.880 0.884 0.880 0.876 0.877 Cetane number 49 46 62 54 63 58 Reference no. [73] [73] [74] [75] [75] [76]
Sunower Soybean Palm Peanut Babassu Tallow
The BD was characterized by determining its density, viscosity, high heating value, cetane number, cloud and pour points, characteristics of distillation, and ash and combustion points according to ISO norms [8]. The higher heating values of the BD fuels, on a mass basis, are 913% lower than no. 2 diesel fuel. The cloud and pour points of no. 2 diesel fuel are signicantly lower than the BD fuels. The BD fuels produced slightly lower power and torque and higher fuel consumption than no. 2 diesel fuel. The properties of BD are close to no. 2 diesel fuels. Some fuel properties of methyl ester BDs are presented in Table 13. Two important parameters for low temperature applications of a fuel are Cloud Point (CP) and Pour Point (PP). The CP is the temperature at which wax rst becomes visible when the fuel is cooled. The PP is the temperature at which the amount of wax out of solution is sufcient to gel the fuel, thus it is the lowest temperature at which the fuel can ow. BD has higher CP and PP compared to conventional diesel [77].
No. 2 diesel fuel Sunower oil Sunower methyl ester Cottonseed oil Cottonseed methyl ester Soybean oil Soybean methyl ester Corn oil Opium poppy oil Rapeseed oil
55 50 Viscosity, cSt 45 40 35 30
48.1 45.5 38.0 37.0 37.6 37.6
25 900
905
910
915
920
925
Density, g/L
Source: Ref. [8]. a Cetane number (CN) is a measure of ignition quality of diesel fuel.
Fig. 11. Relationships between density and viscosity for vegetable oils.
482
4.7 4.5 4.3 4.1 3.9 3.7 3.5 850
4.2. Comparison of fuel properties and combustion characteristics of methyl and ethyl alcohols and their esters Ethanol is an environmentally benign fuel. The systematic effect of ethyl alcohol differs from that of methyl alcohol. Ethyl alcohol is rapidly oxidized in the body to carbon dioxide and water, and in contrast to methyl alcohol no cumulative effect occurs. Ethanol is also a preferred alcohol in the transesterication process compared to methanol because it is derived from agricultural products and is renewable and biologically less objectionable in the environment. Methanol has a higher octane rating than gasoline. Methanol has high heat of vaporization that results in lower peak ame temperatures than gasoline and lower nitrogen oxide emissions. Its greater tolerance to lean combustion higher air-to-fuel equivalence ratio results in generally lower overall emissions and higher energy efciency. However, several disadvantages must be studied and overcome before neat methanol is considered a viable alternative to gasoline. The energy density of methanol is about half that of gasoline, reducing the range a vehicle can travel on an equivalent tank of fuel [8]. In general, the physical and chemical properties and the performance of ethyl esters are comparable to those of the methyl esters. Methyl and ethyl esters have almost the same heat content. The viscosities of the ethyl esters are slightly higher and the cloud and pour points are slightly lower than those of the methyl esters. Engine tests demonstrated that methyl esters produced slightly higher power and torque than ethyl esters [23]. Some desirable attributes of the ethyl esters over methyl esters are: signicantly lower smoke opacity, lower exhaust temperatures, and lower pour point. The ethyl esters tended to have more injector coking than the methyl esters. There are some important differences in the combustion characteristics of alcohols and hydrocarbons. Alcohols have higher ame speeds and extended ammability limits. Pure methanol is very ammable and its ame is colorless when ignited. The alcohols mix in all proportions with water due to the polar nature of OH group. Low volatility is indicated by high boiling point and high ash point. Combustion of alcohol in presence of air can be initiated by an intensive source of localized energy, such as a ame or a spark and also, the mixture can be ignited by application of energy by means of heat and pressure, as it happens in the compression stroke of a piston engine. The high latent heat of vaporization of alcohols cools the air entering the combustion chamber of the engine, thereby increasing the air density and mass ow. This leads to
Viscosity, cSt
860
870 Density, g/L
880
890
Fig. 12. Relationships between density and viscosity for vegetable oil methyl esters.
Previous studies on the effects of BDs on PD fuel lubricity have shown an increase in lubricity associated with the addition of BDs [78,79]. 4.1. Emissions from biodiesel combustion BDs have generally been found to be nontoxic and are biodegradable, which may promote their use in applications where biodegradability is desired. Neat BD and BD blends reduce particulate matter (PM), hydrocarbons (HC) and carbon monoxide (CO) emissions and increase nitrogen oxides (NOx) emissions compared with diesel fuel used in an unmodied diesel engine [80]. The emission impacts of 20 vol.% BD for soybean-based BD added to an average base PD is given in Table 15. Results indicate that the transformities of biofuels are greater than those of fossil fuels, thus showing that a larger amount of resources is required to get the environmental friendly product. This can be explained by the fact that natural processes are more efcient than industrial ones. On the other hand, the time involved in the formation of the fossil fuels is considerably different from that required for the production of the biomass [81]. Coconut BD can yield reductions of 80.8109.3% in net CO2 emissions relative to PD [82].
Table 15 Emission impacts of 20 vol.% BD for soybean-based BD added to an average base PD Percent change in emissions NOx (nitrogen oxides) PM (particular matter) HC (hydrocarbons) CO (carbon monoxide) Source: Ref. [80]. C2.0 K10.1 K21.1 K11.0
483
increased volumetric efciency and reduced compression temperatures [8]. Methanol is not miscible with hydrocarbons and separation ensues readily in the presence of small quantities of water, particularly with reduction in temperature. Since alcohols, especially methanol, can be readily ignited by hot surfaces, pre-ignition can occur. It must be emphasized here that pre-ignition and knocking in alcohol engine is a much more dangerous condition than gasoline engines. Other properties, however, are favorable to the increase of power and reduction of fuel consumption. When diesel engines are converted to alcohols, some properties of gasoline, diesel and alcohol should be concerned. Table 16 shows the characteristic properties of the fuels. Because alcohols have limited solubility in diesel fuel, stable emulsion must be formed that will allow it to be injected before separation occurs. Hydroshear emulsication unit can be used to produce emulsions of diesel-alcohol. 5. Engine performance tests The methyl ester of vegetable oil was evaluated as a fuel in compression ignition engines (CIE) by researchers. They concluded that the performance of the esters of vegetable oil did not differ greatly from PD fuel [61,83]. The brake power was nearly the same as with PD fuel, while specic fuel consumption was higher than PD fuel. Based on crankcase oil analysis, engine wear rates were low but some oil dilution did occur. Carbon deposits inside the engine were normal with the exception of intake valve deposits. Fumigation is a process of introducing alcohol into the diesel engine (up to 50%) by means of a carburetor in the inlet manifold. At the same time, the diesel pump operates at a reduced ow. In this process, BD fuel is used for generating a pilot ame, and alcohol is used as a fumigated fuel. A visual inspection of the injector types would indicate no difference between the BD fuels when tested on no. 2 PD fuel. The overall injector coking is considerably low. Linear regression is used to compare
Table 16 Comparison of characteristic properties of fuels Fuel property Cetane number Octane number Auto-ignition temperature (K) Latent heat of vaporization (MJ/Kg) Lower heating value (MJ/Kg) Gasoline 96 644 0.35 44.0 No. 2 diesel 50 588 0.22 42.6
injector coking, viscosity, percent of BD, total glycerol, and heat of combustion data with the others. Peak torque is less for the BD fuels than diesel fuel but occurs at lower engine speed and generally the torque curves are atter. Test includes the power and torque of the methyl esters and PD fuel and ethyl esters versus PD fuel. The BD fuels on the average decrease power by 5% compared to that of PD at rated load. 6. BD economy The cost of BD fuels varies depending on the base stock, geographic area, variability in crop production from season to season, the price of the crude petroleum and other factors. BD has over double the price of PD. The high price of BD is in large part due to the high price of the feedstock. However, BD can be made from other feedstocks, including beef tallow, pork lard, and yellow grease Fatty acid methyl ester could be produced from tall oil, a by-product in the manufacture of pulp by the Kraft process. Tall oil consists of free C18 unsaturated fatty acids, resin acids and relatively small amounts of unsaponiables [84,85]. The fatty acid fraction of tall oil contains mainly oleic acid, linoleic acid and its isomers. Tall oil fatty acids are easily converted into their methyl esters by reaction with methanol, whereas the resin acids are virtually unesteried due to hindered effect [86]. BD has become more attractive recently because of its environmental benets. The cost of BD, however, is the main obstacle to commercialization of the product. With cooking oils used as raw material, the viability of a continuous transesterication process and recovery of high quality glycerol as a BD by-product are primary options to be considered to lower the cost of BD [10,11]. Vegetable oils are a renewable and potentially inexhaustible source of energy with an energetic content close to PD fuel. The vegetable oil fuels were not acceptable because they were more expensive than petroleum fuels. With recent increases in petroleum prices and uncertainties concerning petroleum availability, there is renewed interest in vegetable oil fuels for diesel engines.
Iso-octane 100 530 0.26 45.0
Methanol 5 112 737 1.18 19.9
Ethanol 8 107 606 0.91 26.7
484
Most of the BD that is currently made uses soybean oil, methanol, and an alkaline catalyst. The high value of soybean oil as a food product makes production of a cost-effective fuel very challenging. However there are large amounts of low-cost oils and fats such as restaurant waste and animal fats that could be converted to BD. The problem with processing these low cost oils and fats is that they often contain large amounts of free fatty acids (FFA) that cannot be converted to BD using an alkaline catalyst [2,87]. A review of 12 economic feasibility studies shows that the projected costs for BD from oilseed or animal fats have a range US$0.30-0.69/l, including meal and glycerin credits and the assumption of reduced capital investment costs by having the crushing and/or esterication facility added onto an existing grain or tallow facility. Rough projections of the cost of BD from vegetable oil and waste grease are, respectively, US$0.54-0.62/l and US$0.34-0.42/l. With pre-tax diesel priced at US$0.18/l in the US and US$0.20-0.24/l in some European countries, BD is thus currently not economically feasible, and more research and technological development will be needed [2,88].
7. Conclusion With exception of hydropower and nuclear energy, the major part of all energy consumed worldwide comes from petroleum, charcoal and natural gas. However, these sources are limited, and will be exhausted on the near future. Thus, looking for alternative sources of energy is of vital importance. Vegetable oils are a renewable and potentially inexhaustible source of energy with an energetic content close to diesel fuel. The vegetable oil fuels were not acceptable because they were more expensive than petroleum fuels. With recent increases in petroleum prices and uncertainties concerning petroleum availability, there is renewed interest in vegetable oil fuels for diesel engines. The purpose of the transesterication of vegetable oils to their methyl esters (biodiesels) process is to lower the viscosity of the oil. The main factors affecting transesterication are molar ratio of glycerides to alcohol, catalyst, reaction temperature and pressure, reaction time and the contents of free fatty acids and water in oils. The commonly accepted molar ratios of alcohol to glycerides are 6:130:1.
Viscosity is the most important property of biodiesel (BD) since it affects the operation of fuel injection equipment, particularly at low temperatures when the increase in viscosity affects the uidity of the fuel. BD has viscosity close to diesel fuels. High viscosity leads to poorer atomization of the fuel spray and less accurate operation of the fuel injectors. The parameters affecting on the methyl esters formation are reaction temperature, pressure, molar ratio, water content and free fatty acid content. It is evident that at subcritical state of alcohol, reaction rate is so low and gradually increased as either pressure or temperature rises. It was observed that increasing the reaction temperature, especially to supercritical conditions, had a favorable inuence on the yield of ester conversion. The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol. In the supercritical alcohol transesterication method, the yield of conversion raises 5095% for the rst 10 min. The BDs have high boiling points, ash points, and extremely low vapor pressure, as well as an inability to smoke under the smoke point test. BD is considered to be an attractive transportation fuel for use in environmentally sensitive applications due to its biodegradable nature, and essentially no sulfur and aromatic contents, offers promise to reduce particulate and toxic emissions. BDs have several outstanding advantages among other new-renewable and clean engine fuel alternatives. Fuel characterization data show some similarities and differences between BD and PD [2]: Sulfur content for BD is 2050% that of D2 fuel Specic weight is higher for BD, heat of combustion is lower, viscosities are 1.32.1 times that of No. 2 PD fuel Pour points for BD fuels vary from 274 to 298 K higher for BD fuels depending on the feedstock The BDs all have higher levels of injector coking than no. 2 PD. A novel process of BD fuel production has been developed by a non-catalytic supercritical methanol method. Supercritical methanol has a high potential for both transesterication of triglycerides and methyl esterication of free fatty acids to methyl esters for diesel fuel substitute. In the supercritical methanol transesterication method, the yield of conversion raises 96% for 10 min.
485
References
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Progress in Energy and Combustion Science 31 (2005) 466487 www.elsevier.

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Total production Amount of vegetable oil, Million ton

Source: World statistics, 19982004 United Soybean Board.

Annual oil consumption, wt%

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

2H2 C CO/ CH3 OH

Source: Ref. [30].

Source: Ref. [7].

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

900 1000 Temperature, K

Yield of hydrogen, vol.%

Source: Refs. [7,57].

Source: Refs. [7,58].

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Yield of methyl ester, wt%

Yield of methyl ester, wt%

Reaction time (sec)

Reaction time (sec)

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Fatty acid alkyl ester, %

60 Methanol 40 Ethanol 1-Propanol 20 1-Butanol 1-Octanol

20 30 Reaction time, min

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Fig. 8. Mechanism of the alkali-catalyzed transesterication of vegetable oils (B: base).

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

100 80 60 40 20 0 0 1 2 3 4 5 Water content, %

100 Methyl ester, % 80 60 40 20 0 0 10 20 Free fatty acid content, % 30

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Sunower Soybean Palm Peanut Babassu Tallow

48.1 45.5 38.0 37.0 37.6 37.6

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

870 Density, g/L

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

Iso-octane 100 530 0.26 45.0

Methanol 5 112 737 1.18 19.9

Ethanol 8 107 606 0.91 26.7

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

A. Demirbas / Progress in Energy and Combustion Science 31 (2005) 466487

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