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��ࡱ�>��	���������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������[�	����bjbj����	$ΐΐ�_"��������**mm���$����PU���3huL����]]]�1�1�1�1�1�1�1$m4�7:�1�]�"@]]�1mm��$�2�+�+�+]�m�mR��1�+]�1�+�+:�0,�"�0��������a�G':�0
�1�203�0.I7�*TI7�0�0I7��0�]]�+]]]]]�1�1�+]]]3]]]]��������������������������������������������������������������������I7]]]]]]]]]*	3:	�Well-to-Wheel Analysis of Future Automotive Fuels and Power trains�
Chetan Ramesh Patil1, Nitin Narayan Sarode2, Prasad Prabhakar Kulkarni3, Lalit Narendra Patil4 Kunal Uday Shinde5
1(Department  of Mechanical Engineering, Sandip Institute if Engg & Managemnt, Nashik .
Email: patilchetan08@gmail.com)
2 (Department  of Mechanical Engineering, Sandip Institute if Engg & Managemnt, Nashik .
Email: nitin.sarode@siem.org.in
3 (Department  of Mechanical Engineering, Sandip Institute if Engg & Managemnt, Nashik .
Email: Prasad.kulkarni@siem.or.in

4(Department  of Mechanical Engineering, Sandip Institute if Engg & Managemnt, Nashik .
Email: lalit.patil@siem.org.in

5(Department  of Mechanical Engineering, Sandip Institute if Engg & Managemnt, Nashik .
Email:kunal.shinde@siem.org.in
ABSTRACT 
The awareness of the effect emissions have on the environment and climate has risen in the last decades. This has caused strict regulations of greenhouse gas emissions. Greenhouse gases cause global warming which may have devastating environmental effects. Most of the fuels commercially available today are fossil fuels. There are two major effects of using fuels with fossil origin; the source will eventually drain and the usage results in an increase of greenhouse gases in the atmosphere. Fuels that are created from a renewable feedstock are often referred to as alternative fuels and under ideal conditions they are greenhouse gas neutral, meaning that the same amount of greenhouse gases is released during combustion as the source of the fuel have absorbed during its growth period. This evaluation method is known as a well-to-wheel analysis which besides emissions also evaluates energy efficiencies during both the production and the combustion phases.


Keywords - Biomass, GHG emission, gasoline products, analysis of these fuels to find new alternative for fossile fuels.

INTRODUCTION
The main calculations have been carried by a software program developed by LBST3 and which combines a database for all input data and their references with an algorithm for the rigorous calculation of the total energy and GHG associated with a given pathway, including feedback loops. 


Each pathway is described to a suitable level of detail including itemised contributions of the different processes. In order to facilitate comparison between sometimes very different pathways the results are also presented according to 5 generic stages: Production and conditioning at source includes all operations required to extract, capture or cultivate the primary energy source. In most cases, the extracted or harvested energy carrier requires some form of treatment or conditioning before it can be conveniently, economically and safely transported. Transformation at source is used for those cases where a major industrial process is carried out at or near the production site of the primary energy (e.g. gas-to-liquids plant). Transportation to EU is relevant to energy carriers which are produced outside the EU and need to be transported over long distances. Transformation in EU includes the processing and transformation that takes place near the market place in order to produce a final fuel according to an agreed specification (e.g. oil refineries or hydrogen reformers). Conditioning and distribution relates to the final stages required to distribute the finished fuels from the point of import or production to the individual refuelling points (e.g. road transport) and available to the vehicle tank (e.g. compression in the case of natural gas). The table below summarises the pathways considered in this study. Energy source Production and conditioning at source Transformation at source Transportation to markets Processing in EU Conditioning and distribution
As the environmental effects of the increase of greenhouse gases in the atmosphere become more and more clear the interest of alternative energy sources increases. A result of this is that the automobile industry is facing tougher emission regulation as time goes. So far this has most often been achieved by more precise control of the engine together with refining of advanced technologies such as exhaust gas recirculation (EGR), variable valve timing (VVT), catalysts, particulate filters etc. But as long as the energy source is of fossil origin there will always be a net distribution of greenhouse gases to the atmosphere. Biomass based fuels, allow a far less distribution of greenhouse gases hence the carbon dioxide released during combustion has been absorbed by the feedstock from which they have been produced by. This creates a circulation of greenhouse gases and thereby the contribution to the greenhouse effect is minimized. This thesis gives an overview of fuel properties and production of alternative, as well as fossil, fuels together with descriptions of combustion technologies.
BIOMASS
Almost any organic material is a potential energy source. Low value products such as sewage or other residues can be transformed to useful fuels. Biomass can be found all over the world and as the oil price rises, the interest for alternative energy sources increases. There are several benefits in using biomass as an energy source, such as reducing the amount of imported oil, improvement of air quality, reducing the greenhouse effect, and other economical benefits. A list of common biomass feedstock is as follows.
� Sewage
� Forestry wastes
� Agriculture residues
� Sugar
� Energy crops
� Vegetable oil
        � Starch
            Fuels
Numerous fuels can be generated from biomass using fermentation, gasification, or digestion. The evaluated fuels in this report are listed below.
� FT-diesel (Chapter 6)
           � Biodiesel (Chapter 7)
� DME (Chapter 8)
� Methanol (Chapter 9)
     � Ethanol (Chapter 10)
� Hydrogen (Chapter 11)
� Biomethane (Chapter 12)
Natural Gas
Natural gas is a clean and highly useful energy source. The gas is generated in a similar way as oil. Because the gas is light, most of the gas oozes up through the ground and in to the atmosphere. If the gas travels through a porous rock and there are layers of hard rock above, the gas will get caught below the surface of the earth.
Composition-The composition of crude natural gas varies considerable depending on where in the world it is extracted. A typical composition is presented in table 3.1. 




Composition of Crude Natural GasMethaneCH470-90%EthaneC2H6 
0-20%PropaneC3H8ButaneC4H10Carbon DioxideCO20-8%OxygenO20-0.2%NitrogenN20-5%Hydrogen SulphideH2S0-5%Rare gasesAr, He, Ne, XetraceTable 3.1. Typical composition of crude natural gas.[4, Natural Gas Supply Association,2006]
3.2 Fuels
The high amount of hydrocarbons makes natural gas an excellent energy source. Some of the fuels that can be generated out of natural gas are listed below.
� Liquefied Natural Gas (LNG, Chapter 13)
� Compressed Natural Gas (CNG, Chapter 13)
� Dimethyl Ether (DME, Chapter 8)
� Hydrogen (Chapter 11)
� Methanol (Chapter 9)
� Liquefied Petroleum Gas (LPG)
Oil-Oil is generated out of organic material which has been digested in an environment without oxygen during millions of years. For a long time oil has been the primary energy source in automobile propulsion systems. The top five producers of oil in 2004, according to [2, EIA, 2006], are presented in a decreasing order in the following list.
� Saudi Arabia
� Russia
� United States
� Iran
� Mexico
Fuels
Fuels which have its origin in oil are:
� Gasoline (Chapter 14)
� Diesel (Chapter 14)
� Liquefied Petroleum Gas (LPG)
� Jet fuel
INTERMEDIATE PRODUCTS
The products presented in this chapter are not used in automotive power trains. They are intermediate products in various production processes.
Synthesis Gas
Production
Synthesis gas contains primarily hydrogen and carbon monoxide. The ratio between the two gases differs, depending on which source the synthesis gas is produced from. The ratio between the gases is of high importance when the synthesis gas is further processed into a propulsion fuel.
Coal to Synthesis Gas
Synthesis gas production from coal can be summarized in the reaction (5.1) according to [13, Rosa, 2005].
C + H2O "! H2 + CO (5.1)
Natural Gas to Synthesis Gas-The production of synthesis gas from natural gas, presented in this subsection can be closer investigated in [9, Svenskt Gastekniskt Center, 2002]. The high amount of

methane in natural gas leads to that the main part of the reaction can be described as follows.
"  Steam reformation
CH4 + H2O "! 3H2 + CO (5.2)
As can be seen in (5.2), the produced synthetic gas has a H2:CO ratio of 3:1. The drawback of this method is that the reaction needs a high amount of energy to occur.
"  Carbon dioxide reformation
CH4 + CO2 "! 2H2 + 2CO (5.3)
This reforming process creates a low ratio between H2 and CO2 which in some cases is desirable. The process can be combined with the steam reforming process to control the ratio of the produced synthesis gas.
"  Partial oxidation-CH4 +12O2 "! 2H2 + CO (5.4)
Unlike the previous processes this reaction is exothermal, resulting in an energy efficient and simple process. The need for oxygen in the process makes it expensive. The outcome ratio is 2 and the emitted heat is 36 kJ/mol. A drawback of this method is that the mixture of hydrogen and oxygen is highly explosive. This technology has not yet been properly investigated which prevents it from making a commercial breakthrough.
� Autothermal reformingCH4 + 2O2 "! 2H2O + CO2 (5.5)CO + H2O "! H2 + CO2 (5.6)
In this process all the reactions (5.2) to (5.6) are active. The final two are exothermal with an emitted energy of respectively 802kJ/mol and 41 kJ/mol. This generates heat which helps the other transformations to occur. The process is often used as a pre- or aftertreatment to generate the desired H2:CO ratio.
Oil to Synthesis Gas
The reaction which generates synthesis gas from oil can be summarized into (5.7) according to [9, Svenskt Gastekniskt Center, 2002]
"CH2 " +H2O "! 2H2 + CO (5.7)
Biomass to Synthesis Gas
Facts presented in this section are collected from [25, S�rensen, 2004]. The content of synthesis gas produced from biomass depends on the feedstock, but also the amount of oxygen available for the reactions to occur. The ratio between the amount of available oxygen and the amount needed to allow a complete burning is called the "equivalence ratio". If the equivalence ratio is lower than 0.1 the process is called a pyrolysis. During pyrolysis the main energy content of the biomass is found in the char and oily residues and only a small amount is found in the gaseous product. In order to maximize the energy content of the produced gas the ratio should lie somewhere in between 0.2 and 0.4. To simplify the reaction chain only the path from cellulose to synthesis gas is considered. The reaction can be summarized into (5.8).
C6H10O5 +12O2 "! 5H2 + 6CO (5.8)
There are many different gasifiers and three of them will be described to illustrate the principles of gasifying wood. The gasifiers not described here works in similarity to either of the three presented below. The interested reader can find detailed information about several gasifiers in [22, Olofsson Nordin S�derlind, 2005].

Updraft Gasifier: 
As can be seen in figure 5.1 wood is fed at the top sinking downwards and the air at the bottom rising through the container creating a counter-flow. Thereby the alias "counter-flow gasifier". At the bottom of the container combustion occurs, meaning that carbon reacts with oxygen creating heat and carbon dioxide. The carbon dioxide rises through the pile, once again reacting with carbon, creating carbon monoxide. At top of the pile water vapor leaves the feedstock and sinks until it reaches carbon, forming hydrogen and carbon monoxide. The water vapor can also react with carbon monoxide which generates hydrogen and carbon dioxide. This reaction is known as the shift reaction and can be performed in both directions in order to adjust the stoichiometric relation between hydrogen and carbon monoxide in the products synthesis gas.


Figure 5.1. Schematic overview of an updraft gasifier
Downward Gasifier:


Figure 5.2. Schematic overview of a downdraft gasifier

The downdraft gasifier follows the same concept as the updraft gasifier with the advantage of delivering a cleaner gas. Figure 5.2 presents a schematic view of the downdraft gasifier.
� Fluidised bed gasifierThe reactions occur very similar to the updraft gasifier with the difference that fluidized sand is located in the reaction chamber. This shortens the process from hours down to minutes due to that the sand grazes the feedstock removing char etc. from the surface of the feedstock allowing a clean surface for further reactions to occur.
MethaneCH450-70%Carbon DioxideCO225-45%WaterH2O2-7%NitrogenN2<2%OxygenO2<2%HydrogenH2<1%Hydrogen SulphideH2S20-
20000ppm
Table 5.1. Typical Composition Of Biogas.[18, Svenskt       Gastekniskt Center, 2002]
Biogas is generated by anaerobic digestion of organic matter. It occurs naturally in swamps, rubbish dumps, septic tanks, and the arctic tundra. Concerning cellulose (C6H10O5) as feedstock, the reaction can be summarized in equation (5.9) and can be divided into the reactions (5.10) to (5.13), according to [25, S�rensen, 2004]. The digestion process is highly complex and is not described in this thesis.
C6H10O5 + H2O "! 3CO2 + 3CH4 (5.9)
C6H10O5 + H2O "! C6H12O6 (5.10)
C6H12O6 "! 2C2H5OH + 2CO2 (5.11)
2C2H5OH + CO2 "! 2CH3COOH + CH4 (5.12)
2CH3COOH "! 2CO2 + 2CH4 (5.13)
Biogas facilities produce heat and electricity for nearby societies and cities. Further refining is necessary to produce useful fuels as biomethane, methanol etc. The low energy content of biogas, as well as its feedstock, hinders any extensive transportation. As a consequence facilities for refining biogas are often in direct contact with biogas production plants.
FT-DieselAliasGTL,BTL,CTLLHV43.9% [MJ/kg] [21,General Motors 2002]Density0.77-0.88.103 [kg/m3] [17, Kalakov Petves,2005] Cetane70-80% [-] [17, Kalakov Petves,2005]Table 6.1. Properties of Ft-Diesel.
FT-Diesel
CO + 2H2 "! "CH2 " +H2O (6.1)
CO + H2O "! H2 + CO2 (6.2)
Several products are generated in the polymerization, such as hydrocarbons (C1- C4), gasoline (C5-C11), diesel (C12-C20), and waxes (>C20). Before the synthesis gas is transported to the FT-reactor the combined sulphur and particle amount has to be less than 1 ppm and the combined presence of nitrogen, carbon dioxide, and methane needs to be below 10%. There are two technologies of FT-processes; low temperature- Fischer-Tropsch, which is used to create greater polymer as diesel, and high-temperature-Fischer-Tropsch to achieve a high amount of lighter hydrocarbons. The outcome of the process is controlled by the Anderson-Schultz-Flory distribution of hydrocarbons and is presented in equation (6.3), completed with a graphical presentation for some interesting chains in figure 6.1. The propagation and termination rates are depending on pressure, temperature, and how long the polymer chain has been in the process. By controlling these parameters the output of the desired product can be maximized. The amplitude of the curves presented in figure 6.1 represents the outcome weight fraction for each chain. The highest exchange is achieved for methane but the highest exchanged for a liquid fuel is diesel which motivates the production of diesel instead of gasoline.

The FT-process is exothermal and requires efficient cooling and temperature control in order to receive the desirable outcome. The gas which leaves the reactor is separated into methane, ethane, ethene, and unreacted synthesis gas. The unreacted gas can be reinserted in the reactor but it is more common that it is burned.




Figure 6.1. Anderson-Schultz-Flory Distribution


Usage and Future Possibilities
BiodieselAliesFAME, RME, SME,B100TypeRMESMELHV37-38 [MJ/kg]32 [MJ/kg]Density0.88.103 [kg/m3]0.87.103 [kg/m3]Cetane Number51-58 [-]46-67 [-]The production cost is higher than that of petro-diesel which is the industrial term for diesel produced from oil. Therefore FT-diesel requires economical assistance from the governments in order to make a commercial breakthrough. The similarity to petro-diesel is a great advantage because the vehicle fleet and infrastructure already exist. FT-diesel is fully compatible with ordinary diesel engines and there is no need for any modifications. As the product is sulphur free and only contains low amount of other impurities the emission is cleaner than that of petrodiesel. In 2001, Sweden carried out a test of FT-diesel and blends with petro-diesel propelling tractors, cars, buses, etc that lasted for 10 months. The emission results showed that all emissions decreased compared to petro-diesel, for example soot or PM (Particle Matter) decreased with 30% and nitrogen oxides (NOx) with 8%. More information regarding this test is presented in [1, FramTidsbr�nslen AB, 2005]
BiodieselAliesFAME, RME, SME,B100TypeRMESMELHV37-38 [MJ/kg]32 [MJ/kg]Density0.88.103 [kg/m3]0.87.103 [kg/m3]Cetane Number51-58 [-]46-67 [-]Table 7.1. Properties of biodiesel. [26, Tse, 2004]

and lower case letters. When referring to a table in the text, no abbreviation is used and "Table" is capitalized.Biodiesel can be produced out of vegetable oils or animal waste. The most common oils used in Europe to produce biodiesel are rapeseed oil and sunflower oil. Today the product is also known as FAME (Fatty Acid Methyl Ester) and can be divided into RME (Rape seed oil Methyl Ester) or SME (Sunflower oil Methyl Ester) which is done in table 7.1. The following emphasized text is an extraction from [16, Tyson, Bozell, Wallace, Petersen, Moens, 2004].
Fatty acids methyl esters are one of two primary platform chemicals produced by the olechemical industry. Methyl esters from triglycerides are produced using inexpensive base catalysts (NaOH or KOH) methanol at low temperatures (60�%C to 80�%C) and pressures (1.4 atm) in both batch and continuous systems. The other major platform chemical, fatty acids, can also be used to produce methyl esters. Fats are hydrolyzed to free fatty acids and glycerol in one of two ways:
"  continuous, high pressure, counter current systems at 20 to 60 bars and 250�%C with or without catalysts, which are typically zinc oxide, lime, or magnesium oxide added to water; "  counter current systems at atmospheric pressure with small amounts of sul- furic/sulfonic acids in steam.
Methyl esters are produced from fatty acids using strong mineral acids, such as sulfuric acid or a sulfonated ion exchange resin, and methanol in counter cur- rent systems at 80�%C to 85�%C under mild pressures. If a feedstock contains triglycerides and free fatty acids, acid esterification is performed on the entire feedstock first, followed by transesterification to convert the remaining triglyc- erides. Water management is a key to high yields and low processing problems. Yields of glycerides and fatty acids to esters for all processes generally exceed 97% and can reach 99% with careful management of equilibrium conditions. corresponds to the percentage of biodiesel present in the fuel.
DMEAliesMethoxymethane, Wood Ether, Dimethyl EtherMoleculeCh3OCH3LHV27.6 [MJ/kg]Density (liquid)0.66.103 [kg/m3]Cetane Number>55 [-]Table 8.1. Properties of DME. [12, Bio-DME Consortium]
Conclusion: 
The facts presented in this report have shown that gaseous fuels have benefits regarding well-to-wheel efficiency and emissions. Biomethane should be produced by organic waste while wood should be transformed to into hydrogen. Taking into account the infrastructural difficulties concerning gaseous fuel this scenario is not likely in a close future. Liquid fuels have great advantages regarding low cost equipment connected to transportation, filling procedure and storage, compared to the equipment needed for handling gaseous fuels. Although hydrogen can be used in ICE engines it will not enter the market until the fuel cells meets the durability and economical demands of the vehicle market. The significantly better well-to-wheel result for biomethane compared to the liquid biomass based fuels will most likely result in an increase usage of biomethane in the next couple of years. However, there is one factor that may hinder the expansion of biomethane usage, and that is the expansion of ethanol usage. Ethanol has the worst wellto- wheel result of all biomass based fuels, but the similarity to gasoline and the access to imported ethanol have caused that filling station companies and the vehicle industry to choose to target ethanol as the primary biomass based fuel. The result of this is that ethanol may hinder expansion of other biomass based fuels. FT-diesel and biodiesel are both worthy supplements for fossil diesel and they may widely enter the market in few years.
References:
 [1] FramTidsbr�nslen AB. Sundsvall demonstration plant - f�rstudie for production av Fischer tropsch diesel. The document is located at http://www.framtidsbranslen.se/bilder/forstudie.pdf, 2005.
[2] Energy Information Administration. HYPERLINK "http://www.eia.doe.gov/emeu/cabs/topworldtables1_2.html.%202006-03-21" .78CEXY[opr���������		#	/	0	2	�	�	�	�	�	�	�	

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����������� �!�"����������
�������f�g��������������������鴬���������������������������&jhE2�hE2�B*CJUaJphh�r,h�I�0JCJaJh�I�h�I�CJaJh�I�CJaJjh�I�CJUaJhE2�hE2�0JCJaJUhE2�hE2�CJaJjhE2�hE2�CJUaJhE2�hE2�B*CJaJphhiv(CJaJ2http://www.eia.doe.gov/emeu/cabs/topworldtables1_2.html. 2006-03-21.
[3] Pavli Polyphone Ari Lampinen and Kari Hanimex. Traffic fuel potential of waste based biogas in industrial countries the case of finland. Technical report, Department of Biological and Environmental Sciences at University of Jyvaskyla, 2004.
[4] Natural Gas Supply Association. www.naturalgas.org. 2006-03-21.
[5] P.C. Badger. Ethanol from cellulose: A general review. 2002.
[6]Batteryuniversity.com. Internet. The document is located at  HYPERLINK "http://www.batteryuniversity.com/partone-3.htm" http://www.batteryuniversity.com/partone-3.htm.
[7] P�l B�rjesson. Energibalans f�r bioetanol - en kunskaps�versikt. Technical Report 59, Department of Technologie and Society at Lund University, March 2006.
[8] Matthew Brusstar and Marco Bakenhus. Economical, high-efficiency engine technologies for alcohol fuels. Internet. The document is located at  HYPERLINK "http://www.methanol.org/pdfFrame.cfm?pdf=ISAF-XV-EPA.pdf" http://www.methanol.org/pdfFrame.cfm?pdf=ISAF-XV-EPA.pdf.
[9] Svenskt Gastekniskt Center. Naturgas som r�vara f�r kemikalier och brainstem, 2002. The document can be downloaded at  HYPERLINK "http://www.sgc.se/rapporter/resources/sgc123.pdf" http://www.sgc.se/rapporter/resources/sgc123.pdf.
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www.ijsret.org


International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 � 0882 
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