Methanol and Gasoline Blending - Automotive

Optimization of low volume Renewable Methanol blending
Chivukula Venkata Kalyan
REYKJAVK ENERGY GRADUATE SCHOOL OF SUSTAINABLE ENERGY
REYST report 09-2011

by C V Kalyan
Thesis Master of Science June 2011
MSc.Thesis20102011

eftir C V Kalyan
Ritger til meistaraprfs (MSc)
Jn 2011
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OptimizationoflowvolumeRenewableMethanolblending
MSc.Thesis20102011

C V Kalyan
Thesis submitted to the School of Science and Engineering at Reykjavk University in partial fulllment of the requirements for the degree of Master of Science June 2011 Supervisors: Dr. Gudrun Arnbjorg Saevarsdottir Assistant Professor, Reykjavk University, Iceland Mr. Kiran Kumar Director, Carbon Recycling International, Iceland Examiner: Dr. Halldor Palsson Associate Professor, University of Iceland, Iceland
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MSc.Thesis20102011

C V Kalyan
Thesis submitted to the School of Science and Engineering at Reykjavk University in partial fulllment of the requirements for the degree of Master of Science
June 2011
Student: ___________________________________________ C V Kalyan
Supervisors: ___________________________________________ Dr. Gudrun Arnbjorg Saevarsdottir ___________________________________________ Mr. Kiran Kumar
Examiner: ___________________________________________ Dr. Halldor Palsson
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ACKNOWLEDGEMENTS
Firstandforemost,IwouldliketothankMr.KCTran,CEO,CarbonRecyclingInternational, Reykjavik, Iceland for giving me an opportunity to pursue my masters thesis research project. I would like to express my sincere gratitude to my supervisor and advisor committee Dr. Gudrun Saevarsdottir, Mr. Kiran Kumar and Dr. Andri Ottesen for giving me guidance,encouragementandmotivation. I would also like to thank Mr. Omar Sigurbjornsson for extending his support to perform laboratoryexperiments.IwanttothankEddaLiljaSveinsdottirforgivingmeanopportunity tobeapartofREYSTtopursuemymastersstudies. DuringmyresearchworkatCRIIhavegainedprofessionalandcorporateexperiencewhich benefitted me with personality development and inspiration to perform. I would like to thankmycolleaguesforsharingprofessionalexperiencesandmotivatingme.
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TableofContents
ACKNOWLEDGEMENTS............................................................................................................................... 6 ABSTRACT................................................................................................................................................. 11 1 INTRODUCTION................................................................................................................................ 12 1.1 1.2 1.3 1.4 1.5 1.6 1.7 2 ORIGINOFFOSSILFUELS.............................................................................................................................. 12 DEPLETIONOFFOSSILFUELS......................................................................................................................... 12 GREENHOUSEGASEMISSIONSANDCLIMATECHANGE....................................................................................... 13 GHGEMISSIONSINICELAND........................................................................................................................ 13 USEOFNONFOSSILFUELS........................................................................................................................... 15 DEVELOPMENTOFBIOFUELS......................................................................................................................... 15 SUMMARY................................................................................................................................................ 17
BACKGROUNDANDPROBLEMSTATEMENT ...................................................................................... 18 2.1 2.2 2.3 2.4 2.5 2.6 RENEWABLEFUELSINICELAND...................................................................................................................... 18 METHANOLASATRANSPORTATIONFUEL ......................................................................................................... 19 HISTORYOFMETHANOLASFUEL.................................................................................................................... 20 PROBLEMSTATEMENT ................................................................................................................................. 21 RESEARCHMETHODOLOGY.......................................................................................................................... 22 SUMMARY................................................................................................................................................ 25
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RMBLENDINGEFFECTSONGASOLINEPROPERTIESSECONDARYRESEARCH .................................... 26 3.1 3.2 3.3 3.4 3.5 OCTANENUMBER...................................................................................................................................... 27 VOLATILITY ................................................................................................................................................ 28 STABILITYANDOTHERS ................................................................................................................................ 31 PHASESTABILITY........................................................................................................................................ 34 SUMMARY................................................................................................................................................ 38
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DEVELOPMENTOFTHEBLENDTESTFACILITYATCRI......................................................................... 40 4.1 ESTABLISHMENTOFBLENDTESTFACILITY........................................................................................................ 41 4.2 QUALITYASSURANCEREPEATABILITY............................................................................................................ 45 4.3 SUMMARY................................................................................................................................................ 47
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RM3BLENDTESTINGEXPERIMENTSANDRESULTS......................................................................... 48 5.1 5.2 5.3 5.4 5.5 5.6 RESULTSFORREIDVAPOURPRESSURE(RVP).................................................................................................. 48 RESULTSFORDISTILLATIONCHARACTERISTICS................................................................................................... 50 RESULTSFORSTABILITYANDOTHERS.............................................................................................................. 53 RESULTSFORPHASESTABILITY...................................................................................................................... 55 SUMMARYOFRESULTS................................................................................................................................ 57 SUMMARY................................................................................................................................................ 60
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6 RM3BLENDOPTIMIZATION.............................................................................................................. 61 6.1 6.2 6.3 6.4 6.5 7 ADDITIONOFCOSOLVENTSFORRVPREDUCTIONSECONDARYRESEARCH............................................................ 61 RVPTESTSWITHCOSOLVENTSFORSUMMERRM3BLENDRESULTS.................................................................. 61 RVPTESTSWITHCOSOLVENTSFORWINTERRM3BLENDRESULTS.................................................................... 65 LOWVAPOURPRESSUREBASEGASOLINESECONDARYRESEARCH...................................................................... 66 SUMMARY................................................................................................................................................ 67
RM3BLENDEFFECTSONENGINEPERFORMANCEANDEMISSIONS.................................................... 68 7.1 7.2 7.3 7.4 7.5 FUNDAMENTALSOFRMGASOLINEBLENDEFFECTSONENGINEPERFORMANCELITERATURESTUDY......................... 69 RMGASOLNEBLENDEFFECTSONENGINETESTRESULTS................................................................................. 69 RMGASOLINEBLENDEFFECTSONENGINEEMISSIONSLITERATURESTUDY.......................................................... 70 RMGASOLINEBLENDEFFECTSONENGINEEMISSIONSTESTRESULTS................................................................. 72 SUMMARY................................................................................................................................................ 74
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RM3BLENDEFFECTSONVEHICLEDRIVEABILITYANDCOMPATIBILITY............................................... 75 8.1 8.2 8.3 8.4 8.5 EFFECTSOFSUMMERRM3ONDRIVEABILITY ................................................................................................... 75 EFFECTSOFWINTERRM3ONDRIVEABILITY .................................................................................................... 76 DRIVEABILITYOFTHEVEHICLESWITHRM3ASFUELLITERATURESTUDY.............................................................. 78 COMPATIBILITYOFRM3WITHFUELSYSTEMS.................................................................................................. 78 SUMMARY................................................................................................................................................ 88
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CONCLUSIONANDRECOMMENDATIONS.......................................................................................... 90 9.1 CONCLUSIONS........................................................................................................................................... 90 9.2 RECOMMENDATIONS.................................................................................................................................. 92
REFERENCES.............................................................................................................................................. 96 APPENDIX ................................................................................................................................................100 EXPERIMENTALPROCEDURES............................................................................................................................... 100 SAFETYREQUIREMENTS....................................................................................................................................... 107

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ListofFigures
FIGURE1WORLDFOSSILFUELCONSUMPTION ................................................................................................................ 12 FIGURE2CURRENTANDPROJECTEDSHAREOFBIOFUELSINTRANSPORTATIONSECTOR........................................................... 16 FIGURE3CRISPROCESSSTEPSFORPRODUCINGRENEWABLEMETHANOL.......................................................................... 19 FIGURE4COMPARISONOFFUELPROPERTIESOFMETHANOL,ETHANOLANDGASOLINE ........................................................... 20 FIGURE5EFFECTSOFALCOHOLADDITIONTOGASOLINERVP(1PSI=7KPA)........................................................................ 28 FIGURE6SAMPLEDISTILLATIONCHARACTERISTICSOFGASOLINE........................................................................................ 29 FIGURE7EFFECTOFALCOHOLADDITIONTOGASOLINEDISTILLATION.................................................................................. 30 FIGURE8WATERTOLERANCEOFGASOLINEMETHANOLBLENDS(330%MEOH).................................................................. 36 FIGURE9RVPTESTFACILITY ....................................................................................................................................... 42 FIGURE10DISTILLATIONCHARACTERISTICSTESTFACILITY................................................................................................. 43 FIGURE11WATERCONTENTTESTFACILITY .................................................................................................................... 44 FIGURE12COOLINGFACILITY..................................................................................................................................... 44 FIGURE13RVPOFBASEGASOLINE&RM3(SUMMER)................................................................................................... 49 FIGURE14RVPOFBASEGASOLINE&RM3(WINTER).................................................................................................... 50 FIGURE15DISTILLATIONCURVEOFBASEGASOLINEVSRM3(SUMMER)............................................................................. 52 FIGURE16DISTILLATIONCURVEOFBASEGASOLINEANDRM3(WINTER)............................................................................ 53 FIGURE17RVPRESULTSFORRM3BLEND+(15%)OFETHANOL.................................................................................... 62 FIGURE18RVPRESULTSFORRM3BLEND+(13%)OF1PROPANOL............................................................................... 63 FIGURE26CO,HCANDNOXEMISSIONSAT~2500RPMFORGASOLINE,RM3ANDRM10................................................ 73 FIGURE26WATERTOLERANCEOFGASOLINEWITHCOSOLVENTS...................................................................................... 94

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ListofTables
TABLE1R/PRATIO'SOFMAINFOSSILFUELS _________________________________________________________13 TABLE2TOTAL EMISSIONSOFGHGBYSOURCESINICELANDIN19902008,CO2EQ.___________________________14 TABLE3LEGALREQUIREMENTSOFGASOLINEPROPERTIESINICELANDANDIDENTIFICATIONOFPROPERTIESTHATCANBEEITHER CALCULATEDORREQUIREDEXPERIMENTATIONFORMEASUREMENTSAFTERRMBLENDING. _____________________23 TABLE4METHANOLSOLUBILITYBASEDONGASOLINECOMPOSITION _________________________________________35 TABLE5REQUIREMENTANDTESTMETHODSFORUNLEADEDPETROL _________________________________________40 TABLE6TESTSTANDARDSFORRM3BLENDPROPERTIESMEASUREMENT ______________________________________41 TABLE7REPEATABILITYTESTRESULTSOFVAPOURPRESSUREEQUIPMENT______________________________________45 TABLE8REPEATABILITYRESULTSFORDISTILLATIONCHARACTERISTICS _________________________________________46 TABLE9RVPRESULTSFORSUMMERBASEGASOLINE ___________________________________________________48 TABLE10RVPRESULTSFORSUMMERRM3_________________________________________________________48 TABLE11RVPRESULTSFORWINTERBASEGASOLINE ___________________________________________________49 TABLE12RVPRESULTSFORWINTERRM3__________________________________________________________49 TABLE13RESULTSFORDISTILLATIONCHARACTERISTICSOFGASOLINE(SUMMER)_________________________________51 TABLE14RESULTSFORDISTILLATIONCHARACTERISTICSOFRM3(SUMMER)____________________________________51 TABLE15RESULTSFORDISTILLATIONCHARACTERISTICSOFBASEGASOLINE(WINTER)______________________________52 TABLE16RESULTSFORTHEDISTILLATIONCHARACTERISTICSOFRM3(WINTER) __________________________________53 TABLE17RESULTFORCOPPERSTRIPCORROSIONFORSUMMERANDWINTER ___________________________________54 TABLE18RESULTFOREXISTENTGUMCONTENTFORSUMMERANDWINTER ____________________________________54 TABLE19RESULTFOREXISTENTGUMCONTENTFORSUMMERANDWINTER ____________________________________54 TABLE20PHASESEPARATIONRESULTSFORSUMMERRM3ATROOMTEMPERATURE ______________________________55 TABLE21PHASESEPARATIONRESULTSFORSUMMERRM3AT300C ________________________________________56 TABLE22PHASESEPARATIONRESULTSFORWINTERRM3ATROOMTEMPERATURE_______________________________56 TABLE23PHASESEPARATIONRESULTSFORWINTERRM3AT300C _________________________________________56 TABLE24COMPILATIONOFRESULTSFORSUMMERRM3_________________________________________________58 TABLE25RESULTSFORWINTERRM3(EN228SPECIFICATIONS) ___________________________________________59 TABLE26RESULTSFORSUMMERRM3WITHCOSOLVENTS_______________________________________________65 TABLE27RESULTSFORTHERM3BLENDSWITHCOSOLVENTSFORWINTERGASOLINE _____________________________66 TABLE28INTROMETSDATAONRVP(INKPA)OFBASEGASOLINEANDFINALBLENDS____________________________67 TABLE29EMISSIONSAT~2500RPM_____________________________________________________________72 TABLE30EMISSIONSAT~5000RPM_____________________________________________________________73 TABLE31VAPOURLOCKINDEXRESULTSFORWINTERRM3 _______________________________________________77 TABLE32ELASTOMERSRESISTANCETOMETHANOL,ETHANOLANDGASOLINEDESIGNOFFLEETTESTINGPROGRAM__________80 TABLE33PARTICIPANTSOFFLEETTESTINGPROGRAMANDDUTIES __________________________________________81 TABLE34ACCEPTABILITYRESULTSFORSUMMERANDWINTERRM3 _________________________________________90 TABLE35RVPRESULTSFORSUMMERRM3WITHCOSOLVENTS ___________________________________________91 TABLE36PHASESEPARATIONOFMETHANOLGASOLINEBLENDSATSPECIFIEDTEMPERATURESWITHWATERCONTENT ________93
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ABSTRACT
IcelandaspartofEuropeanEconomicArea(EEA)isboundtodeveloprenewableenergyfor thetransportationsector.InIcelanditislessfeasibletodevelopbiofuelsfrombiomassthan in warmer climatic regions. Carbon Recycling International (CRI) is producing Renewable Methanol (RM) from geothermal sources in Iceland via recycling CO2 through its patented technology. RM can beused as fuel in gasoline vehicles through directblending to gasoline at high or low level blends. CRI is planning to blend RM into gasoline at 3% volume, to developanRM3blend,asallowedinEuropeanandIcelandiclegislationandstandards. Methanol has a long history of use in racing vehicles where it is valued both for its power producing properties and its safety aspects. There was significant interest in using methanolasagasolineblendingcomponentforitshigheroctanevalueandloweremissions characteristics, which makes it a very attractive fuel or fuel blend for Spark Ignition (SI) engines, in the U.S. when lead was phased out of gasoline. During the 1980s and through much of the 1990s, most gasoline in Western Europe contained a small percent of methanol. Today, China is the leader in using methanol as a transportation fuel where between3and5milliontonswereusedlastyear. InordertoimplementRM3blendasafuelinthemarket,itisimperativetounderstandthe detailed blend specifications and the influence of the blend on vehicle performance. The firstobjectiveofthecurrentresearchistodetermineiftheRM3blendmeetsthenecessary requirements of gasoline fuel in Iceland. The second objective is to look into the technical methodology and optimization of RM3 blend as necessary. The third objective of the researchistoperformsecondaryresearchandteststounderstandthevehicleperformance onRM3blendsforacceptability. RM3 for summer and winter was prepared and tested at laboratory developed at CRI. Optimization techniques were also identified and tested. Engine tests were conducted on RM3 for engine performance, driveability and emissions. Test results were reviewed and validated with literature. Further a fleet test program was designed as part of the research forimplementation.
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1 INTRODUCTION
1.1 ORIGINOFFOSSILFUELS
Fossil fuels are formed from dead organisms buried under layers of mud, soil and rock decomposed into organic material that transform into fossil fuels under different temperaturesandpressures.Themainfossilfuelsaregasoline,diesel,naturalgasandcoal. In todays world fossil fuels are the major source of energy. Due to the rapid increase in global economic development, demand for energy from oil has increased. Since 1950 the consumptionoffossilfuelsquadrupledfrom~2000Mtoeto~8000Mtoeperyear.
Figure1Worldfossilfuelconsumption
The figure 1 is taken from the website article colossal energy consumption and the environment(Anon.,(n.d.))[1]. In particular, the transportation sector accounts for a larger share of fossil fuel utilization. The Transportation sectors share of the oil consumption increased from 45.4% in 1973 to 61.2%in2007(Rodrigue,JP.(n.d.))[2]. 1.2 DEPLETIONOFFOSSILFUELS
Increased extraction of fossil fuels from the earths crust is causing depletion of the finite available resources. Reserve to Production (R/P) ratio is a measure of availability of resources in years. The statistical review of world energy in 2010 by British Petroleum predicts that the oil reserves will be depleted within approximately 45 years with rate of consumption(table1).
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Table1R/Pratio'sofmainfossilfuels Fuel Oil

(Thousandmilliontonnes)
Reserves 181.7 826001.0 6621.2
R/Pratio(Years) 45.7 119.0 62.8
Coal
(milliontonnes)
Naturalgas
(Trillioncubicfeet)
Thedatafortable1istakenfromthewebsitedocumentstatisticalReviewofworldEnergy, (BritishPetroleum,June2010)[3].
1.3
GREENHOUSEGASEMISSIONSANDCLIMATECHANGE
Accumulation of greenhouse gases in the atmosphere has risen the earths temperature, leading to hotter periods in last couple of decades. Increase in earths temperature is the major cause for melting of polar ice caps and glaciers. Increased melting will cause sea levels to rise and submerging of landmass, posing threat to the mankind and nature. Melting of polar ice is feared to cause extinction of some of the species. Also, change in climatepatternswillhaveenvironmental,socialandeconomicalimpacts. Stepsweretakentoaddressclimatechangein1992UnitedNationsFrameworkConvention on Climate Change (UNFCCC) and the 1997 Kyoto Protocol. Especially, European Union has laidroadmapstoimplementpoliciesandmeasurestocheckthegreenhousegasemissions. EU25 countries are signatories of Kyoto Protocol adopted in 1997. Signatories to protocol are bound to reduce green house gas emissions viz. carbon dioxide, methane, nitrous oxide, hydro fluorocarbons, per fluorocarbons and sulphur hexafluoride by 5.2% below the emissionsof1990by2012. 1.4 GHGEMISSIONSINICELAND
The 1992 United Nations Framework Convention on Climate Change (UNFCCC) was ratified by Iceland in 1993 and entered into force in 1994. In 1995 the Government of Iceland adopted an implementation strategy based on the commitments of the Framework Convention.(Anon.,DepartmentofEnvironment,(2007))[4].
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The domestic implementation strategy was revised in 2002, based on the commitments of the Kyoto Protocol. Iceland acceded to the Kyoto Protocol on May 23rd 2002. The Kyoto Protocol commits the signatory parties to individual, legally binding targets for their greenhouse gas emissions in the commitment period 2008 2012. (Anon., Department of Environment,(2007))[4]. One of Icelands main obligations according to the Kyoto Protocol is that for the first commitment period, from 2008 to 2012, the greenhouse gas emissions shall not increase more than 10% from the level of emissions in 1990. However, under decision 14/ CP.7 Impact of single project on emissions in commitment period allows Iceland to report the industrial emissions separately. The limit for carbon dioxide emissions shall not exceed 8,000,000tonnes.(Anon.,DepartmentofEnvironment,(2007))[4]. Total GHG emissions in 1990 in Iceland were 3415 CO2eq. According to the Kyoto commitment, total GHG emissionsmust not increase 10%from 1990 i.e. 3756.5 CO2eq. by 2012.However,IcelandstotalGHGemissionswerealready43%greaterthan1990levelsin 2008 (4880 CO2 eq.). From the table 2 it can be seen that one of the major contributors of GHG emissions is combustion from fuel. (Hallsdttir, Harardttir, Gumundsson, Snorrason,&rsson.(2010))[5].
Table2Total emissionsofGHGbysourcesinIcelandin19902008,CO2eq. Source Fishing+transport Geothermalenergy Industrialprocesses Solventandotherproductuse Agriculture Waste Total 1990 1717 67 863 14 575 180 3415 1995 1837 82 535 14 542 194 3204 2000 1890 163 946 15 552 201 3766 2005 1978 123 917 16 498 194 3727 2006 2022 156 1334 9 528 213 4263 2007 2083 152 1484 12 551 226 4508 2008 1906 185 1992 9 566 221 4880
The data in the table 2 is taken from the website document Iceland greenhouse gas emissions,(Hallsdttir,Harardttir,Gumundsson,Snorrason,&rsson.(2010))[5].
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1.5
USEOFNONFOSSILFUELS
Researchers, environmentalists and policy makers are keen to reduce the dependency on the usage of the polluting fossil fuel. Use of nonfossil fuels such as biofuels can reduce dependencyontheimportofthefossilfuels.Furthernonfossilfuelsorrenewablefuelswill generate very low life cycle GHG emissions compared to fossil fuels. Different kinds of biofuels are available. Biofuels by composition are alcohols, ethers, esters etc. Commonly available biofuels are ethanol, methanol and biodiesel etc. They can be produced from variousthermochemicalandbiochemicalprocesses. The recent directives of the European Union related to transportation sector are aimed to reduce thedependency on imported fossil fuels and increase the utilization of energy from renewable energy sources. Development of renewable sources of energy also plays an important role in promoting the security of energy supply. Directive 2009/28/EC of The European Parliament and of the Council stipulates the member states of the EU to achieve a target of 10% of renewable energy to be used in the transportation industry by 2020. (Anon.,EuropeanParliament,(2009))[6]. 1.6 DEVELOPMENTOFBIOFUELS
In the figure 2 it can be seen that by the end of year 2006 there was only 3% share of biofuelsinthetransportationsectorbutitisexpectedtoriseto6.5%byyear2012and8.5 %by2015.
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Figure2Currentandprojectedshareofbiofuelsintransportationsector
Thefigure2istakenfromtheBritishPetroleumwebsiteforalternativefuels.Thisfigure showstheworldstransportationfuelusage(Anon.,(n.d.))[7]. The report from Global Biofuel Market Analysis estimates that the 87% of total worlds biofuel production is from USA and Brazil. It is estimated by the members of OECD (Organization for Economic Cooperation and Development) and United Nation Food and Agriculture Organization that global ethanol production will double between years 2007 2017 to 125 billion litres and production of biodiesel to increase from 11 billion litres to 24 billionlitres. China National Cereals, Oils and Foodstuff Corp. (COFCO) is investing USD 6.5 million towards building cellulosic ethanol pilot plant. India accounts for almost 4% of global ethanol production, production of ethanol is from sugarcane and biodiesel from jatropha seeds. British Petroleum with Associated British Foods is developing a $400 million world scalebioethanolfacility.(Anon.,(n.d.))[8]. While ethanol and biodiesel constitute the majority of biofuels today new type of fuels are being researched to increase the diversity and improve the biofuel penetration into the market. For example British Petroleum is building 20,000 liters per year biobutanol demonstration plant and is in partnership with academia and joint ventures to develop the technologiesforproductionofvariousbiofuels.(Anon.,(n.d.))[7].
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1.7
SUMMARY
The consumption of fossil fuels increased four times from 1950 to 2008. Transportation sector accounts for majority of the fossil fuel consumption in the world today. With increased consumption of fossil fuels it is expected that the total known reserves will be depleted soon. The increased GHG emissions from the combustion of the fossil fuels have environmental,socialandeconomicimpacts. Renewable fuels and biofuels can reduce dependency on the fossil fuels and reduce GHG emissions. Presently, major producers of biofuels are USA and Brazil. Efforts are being made to increase biofuel production in Europe and Asia. The European Union has laid a road map towards the reduction of GHG emissions and development of renewable fuels andbiofuelsinthetransportationsector. Iceland, being a part of EEA, is committed to support the development of renewable fuels in the transportation sector and thus in this process also reduce the GHG emissions as a partofitsKyotocommitment.

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2 BACKGROUNDANDPROBLEMSTATEMENT
2.1 RENEWABLEFUELSINICELAND
Iceland is a part of European Economic Area and is bound to the European regulations towards development of renewable energy in transportation sector. Both ethanol and biodiesel, the currently most accepted and utilized renewable fuels are produced from biomass such as energy crops, wood and vegetable oil. Weather conditions in Iceland are notidealforgrowingenergycropstoproduceeitherethanolorbiodiesel. However, several steps are being taken to reduce dependency on fossil fuel. Ethanol is being imported into Iceland since 2007 and sold as a high volume blend (E85). Biodiesel is alsobeingimportedsince2004andblendedwithdiesel. Efforts are being made to produce local renewable fuels. Methane is being produced from waste landfills by SORPA and is being used as alternative fuel in a very small fraction of vehiclesinIceland. Carbon Recycling International (CRI) has initiated production of Renewable Methanol (RM) by utilizing renewable geothermal sources in Iceland. In CRI, Renewable Methanol is produced from CO2 using its patented technology. CO2 for the process can be captured from various emission sources such as aluminium smelters, geothermal power plants. The chemical equation and process steps of producing Renewable Methanol from CO2 are shownbelow:

(1) (2) (3)

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Figure3CRIsprocessstepsforproducingRenewableMethanol
Thefigure3istakenfromthewebsiteCarbonRecyclingInternational.Thisfigureshowsthe schematicoftheproductionofRManditsuse(Anon.,(n.d.))[9]. CRI is currently constructing a plant on industrial scale which is expected to produce 5 million litres of Renewable Methanol per year and shall be completed by mid 2011. Upon the success of the industrial scale plant, CRI is further planning to build commercial scale plantswith production capacitiesof~50100millionlitresperyearofRenewableMethanol from2013.(Anon.,(n.d.))[9] RMcanpotentiallybeasustainablesourceofrenewablefuelforbothIcelandandEurope. 2.2 METHANOLASATRANSPORTATIONFUEL
Methanol has certain positive properties which could be used in some way as a potential fuel. Though, neat methanol cannot be used directly in the conventional vehicles because difficulties associated with volatility and material compatibility, but it could be used as a blend with gasoline for its characteristics such as high octane number and lower emissions from vehicles. Methanol is harder to ignite; it burns more slowly and emits lower radiant energy. Following are the main benefits of using methanol as a transportation fuel: (CassadyE.Philip(1975))[10]. 1. Low emissions: Methanol fuelled vehicles have lesser emissions of carbon monoxide and total hydrocarbon emissions and particulate matter from the exhaust of the vehiclesascomparedtothegasolineanddieselfuelledengines.
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2.
Octane Number: Methanol is used as a motor racing fuel for its high antiknock property. Methanol has high blending octane value (BOV).Blending the lower Octane Numberfuelwiththemethanolwilleffectivelyincreasetheoctanenumberofthefuel. Methanols allowance for higher compression ratios results in higher output from the combustionofthefuel. Volatility: Methanol is a volatile substance, it readily evaporates. Methanol could be used as a good volatile substance for the gasoline methanol blend. However, excess volatilitycausesdriveabilityproblemsincarburettorengines.
3.

Figure4Comparisonoffuelpropertiesofmethanol,ethanolandgasoline
Thefigure4isfromresearchpaperProperties,Performance,andemissionsofmethanol gasolineblendsinasparkignitionengine(Qi,Liu,Zhang,Bian,(2004)[11] 2.3 HISTORYOFMETHANOLASFUEL
During 1980s methanol flexiblefuel vehicles (FFVs) were developed which could run on different gasoline and methanol mixtures. FFVs were developed to run on both the fuels depending on the availability of the fuel. In 1988 California Energy Commission (CEC) established the California Fuel Methanol Reserve to increase the availability of the methanol. The agency entered in 10years lease with the ARCO, Chevron, Exxon, Mobil, Shell and Texaco for the installation of methanol storage tanks. By 1990s the number
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increased to 15,000 vehicles in California, by 1993, 12 million gallons of methanol was consumedasatransportationfuel. FourmodelsofFFVssucceededtomakeittotheproductionlevel: 1. FordTaurus 2. ChryslerDodgeSpirit/PlymouthAcclaim 3. ChryslerConcorde/Intrepid 4. GeneralMotorsLumina In Europe a small percent of methanol was added along with the cosolvents to mitigate the properties of gasoline when lead was removed from gasoline due to health and environmentalreasons.Themaximumpermissiblelimitofmethanolingasolineblendis3% % v/v. Gasoline Methanol blending was first used in Germany in 1968, the gasoline available at that time contained 23 % of the methanol along with cosolvents present, by theendof1990thegasolineavailableintheEuropecontained23%ofmethanol.Laterthe directives of the European Economic Community authorized low blend up to 3%. Gasoline fuel in the EEA region follows EN 228 standard. It is an official document drafted by European Committee for standardization of fuels. (Bechtold, Goodman & Timbario) (2007)) [12]. 2.4 PROBLEMSTATEMENT
Currently, CRI is planning to perform low volume blending of Renewable Methanol into gasolineupto3%,introducingRenewableMethanolgasolineblendRM3intothemarket. Iceland imports all of its gasoline which complies with the EN228 standards. However, all the gasoline entering Iceland has to be legally compliant to Icelandic law (nr. 560/2007). Blending of RM would result in change of properties of the base gasoline. The first objective of the current research is to determine if the RM3 blend meets the legal requirementsofgasolinefuelinIceland. Basegasoline(97%)+RM(3%)RM3tomeetnr.560/2007 In case the RM3 blend does not meet legal requirements in Iceland there is a possibility of technically bringing back the blend to legal requirements through addition of cosolvents
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and additives. The second objective is to look into the technical methodology and optimizationofRM3blendtomeetthelegalrequirementsinIceland. Basegasoline(x%)+cosolvents(y%)+RM(3%)RM3tomeetnr.560/2007 While the RM3 blend meets necessary legal requirements it is imperative for the blend to be compatible with the existing vehicle technology and infrastructure. RM3 as a fuel in the vehicles may affect the engines performance, driveability, compatibility and emissions. Thus, the third objective of the research is to conduct secondary research and tests to be conductedtodeterminetheeffectsofRM3blendonengines. 2.5 RESEARCHMETHODOLOGY
2.5.1 Firstobjective Thetable3showsthelistofallthepropertiesofthegasolinewhicharelegalrequirements in Iceland. Blending of RM into gasoline will bring change in properties of the RM3 blend. However, some of the property changes can be calculated directly by knowing the RMs andgasolinesqualityandquantity.Forexamplegivenbenzenecontentof0.8%V/Vinbase gasoline and 3% of RM added to it the final content of benzene in RM3 would be 0.8/1.03=~0.78%V/VassumingnobenzenecontentinRM.Thismethodologywillapplyfor allthepropertieswhosechangescanbecalculateddirectlymentionedinthetablebelow. Theremainingpropertieswhichcannotbecalculateddirectlywouldneedexperimentation. Especially, it is to be noted that at small volumes of methanol blended into gasoline it would mix nonlinearly forming an azeotropic mixture and thus making even some simple properties like density nonlinear and can only be obtained through experimentation. All the properties that need experimentation for measurement after RM blending are shown inthetablebelow.

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Table3LegalrequirementsofgasolinepropertiesinIcelandandidentificationofpropertiesthat canbeeithercalculatedorrequiredexperimentationformeasurementsafterRMblending.
Property
Units Min
Limits Max
ChangeinProperties Direct calculation

9 9 9 9 9 9 9 9 9 9 9 9 9
Experimenta tion
9 9 9 9 9
ResearchOctaneNumber MotorOctaneNumber Vapourpressure,summerperiod Distillation: Percentageevaporatedat100oC Percentageevaporatedat150oC Hydrocarbonanalysis Olefins Aromatics Benzene Oxygencontent Oxygenates Methanol Ethanol isoprpylalcohol tertbutylalcohol isobutylalcohol etherscontaining5ormore carbonatomspermolecule otheroxygenates Sulphurcontent Leadcontent
kPa %V/V %V/V %V/V %V/V %V/V %m/m %V/V %V/V %V/V %V/V %V/V %V/V %V/V Mg/kg g/l
95 85 46 75
70 18.0 35.0 1.0 2.7 3 5 10 7 10 15 10 10 0.005

The data in the table 3 is taken from the Icelandic fuel regulation document In. Nr. 560/2007[13]. Further important properties related to fuels such as existent gum content, copper strip corrosion and oxidation stability which are currently not regulated by law also cannot be calculated directly. To complete the first objective it is thus necessary to perform experimentstodeterminetheRMblendingeffectongasolineproperties. 2.5.2 Secondobjective After performing the experiments based on the first objective there might be some properties identified which do not comply with the regulation. It is very important to
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ensurethattheRM3blendmeettheregulation.Thus,thepossibilitiesofbringingtheblend incompliancewiththeregulationsareexploredandexplainedbelow. By implementing technical methods the properties that are offspec can be controlled in compliance with the regulations. For example an increase in vapour pressure can be brought down by using higher alcohols as cosolvents and increase in corrosion levels can becontrolledbyusingcorrosioninhibitors. After identifying the technical methods relevant cosolvents or additives shall be obtained based on existing literature and shall be tested by using the same experimentation methodology from the first objective. In case of multiple options of reaching the final objective, optimization shall be performed to identify the best technical solution based on costandeaseofimplementation. 2.5.3 Thirdobjective WhilethefirstandsecondobjectivesarefocussedontheRM3blendspecification,itis quiteessentialtostudytheeffectsofRM3blendson: Engineperformance 1. Methanol has lower energy content (16 MJ/L) than that of gasoline (32 MJ/L). However, as studied earlier using methanol as transportation fuel has certain advantages especially with its high octane rating and efficient combustion. Thus, it would be advantageous to study engine performance parameters such power output, torque, Break Mean Effective Pressure (BMEP), Basic Specific Fuel consumption(BSFC)etc.(Bechtold,Goodman&Timbario)(2007))[12]. 2. Driveability Driveability of a vehicle is mainly affected by the volatility of the fuel. RM3 blend has different volatility characteristics than the base gasoline. Thus, it is essential to review the RM3 performance on driveability issues like cold start, vapour lock and heatsoakbacketc. 3. Materialcompatibility Methanol is a corrosive chemical substance. There are concerns regarding the use of methanol as a fuel in the vehicles for compatibility issues with fuel system
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materials. Thus, it is essential to study the compatibility of RM3 in the existing infrastructure. Furthertestsshallbeidentifiedandplannedtoperformindepthanalysisforeffectsonthe enginesifnecessary. 2.6 SUMMARY
Iceland is developing renewable fuels for the transportation sector. Unlike most other countries,InIcelanditislessfeasibletodevelopethanolandbiodieselfrombiomassdueto its weather conditions. CRI in Iceland is producing Renewable Methanol (RM) from geothermal sources from its patented technology. CRI is planning to use RM as a blend in gasoline for up to 3% by volume, making an RM3 blend product. RM can be used as an automotive fuel because of its positive fuel properties. Blending of RM in gasoline will change the properties of the blend. The properties of the final RM3 blend should meet the legislationrequirementsinIceland. Theproblemstatementforcurrentresearchisdividedintothreeareas: 1. To determine if the RM3 blend meets the legal requirements of gasoline fuel in Iceland. 2. To look into the technical methodology and optimization of RM3 blend to meet the legalrequirementsinIceland. 3. To conduct secondary research and tests have to be conducted to determine the effectsofRM3blendonengines. Properties of RM3 blend were identified which can be calculated by direct methods or experimentation.
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3 RM BLENDING EFFECTS ON GASOLINE PROPERTIES SECONDARYRESEARCH

Gasoline fuel is a mixture of hydrocarbons, alcohols, oxygen, sulphur, olefins and Alkenes etc. Boiling point of gasoline ranges from 250C to 2000C. The properties of the gasoline i.e. volatility, density, viscosity vary with the quantity of the elements of the mixture which amounttogasoline. Due to the addition of RM into gasoline some properties of the gasoline methanol blend may change. The intention behind the RM3 samplespecification analysis is to investigate andidentifyanypossiblechangesinthepropertiesofthefuel.Themajorareaswheretests aretobeconductedtoinvestigateandidentifyanypossiblechangeinthefuelblendareas follows(In.Nr.560/2007)[13](Anon.,(2008))[14]. Octanenumber(Legislationrequirement) o ResearchOctaneNumber(RON) o MotorOctaneNumber(MON) x Volatility(Legislationrequirement) o VapourPressure,summerperiod o Distillation Percentageevaporatedat100oC(E100) Percentageevaporatedat150oC(E150) x Stabilityandothers(CRIsinterestformarketentry) o Oxidationstability o ResidueandExistentgumcontent o Copperstripcorrosion o FinalBoilingPoint x Phasestability(CRIsinterestformarketentry) o Watercontent o Phasestabilityatroomtemperature o Phasestabilityatlowtemperature Thepropertieslistedabovecannotbecalculatedtheoreticallyfromthespecificationsofthe basegasolinefuel.So,itisnecessarytoconductpracticaltestsonthefuelblendsamples. x
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3.1
OCTANENUMBER
Octane number is a measure of gasolines resistance to auto ignition. Auto ignition in the enginecouldleadtononuniformcombustionandthusvibrationscouldpotentiallydamage theengine.Thisphenomenoniscalledknocking. RON: Research Octane Number is an indicator of the fuels antiknock performance at lowerenginespeedandtypicalaccelerationconditions. MON: Motor Octane Number is an indicator of the fuels antiknock performance at higher enginespeedsandhigherloadconditions. Referencespecification In nr. 560/2007 regulation of Iceland (In. Nr. 560/2007) [13] minimum octane number of fuelisgivenat95forRONand85forMON ChangeinpropertyduetoRMblending Alcohols and ethers in general have high antiknock properties and for this reason they are specifically used in gasoline to provide higher efficiencies. Methanol being the smallest alcohol has one of the highest octane rating among the existing oxygenates that are allowed for blending in gasoline. Flame propagation in methanol is even, making the combustioncharacteristicseven. Methanol has higher octane ratings of RON and MON than the legislation requirements. Even though the final octane number of a given blend need not necessarily be a linear calculation the final effect of the blending tends to be towards the linear calculation. Thus, based on the above data and practical tests performed from literature it can be concluded that blending of RM in existing gasoline which already meets the legislation requirements willhaveapositiveeffectontheoctanenumber. PurposeofmeasurementforRMblend Based on the above discussion RM3 blend would definitely meet the necessary legislation requirements for octane rating. Thus, for the purpose of this study it is identified that measurementofoctanenumberofRM3blendisnotrequired.
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3.2
VOLATILITY
The tendency of the fuel to vaporise is called volatility and the main measures of the volatilityofthefuelarevapourpressureanddistillationcharacteristics. 3.2.1 VapourPressure(alsoknownasReidVapourPressureRVP) Definition Itisvapourpressureofthefuelatstandardtemperatureof37.8oCinvacuum. Referencespecification In nr. 560/2007 regulation of Iceland (In. Nr. 560/2007) [13] vapour pressure is required to be at a maximum of 70 kPa for summer periods. Summer period is defined to be period betweenJulytoAugust. ChangeinpropertyduetoRMblending RVP of pure RM is about 32kPa. Gasoline has RVP of about 4570 kPa during summer. However, blending 3% of RM in gasoline will increase theRVP of the gasoline by upto 35% this is due to the fact that methanol forms nonlinear mixture with gasoline. The actual increase in the RVP is of course determined by the nature of the base gasoline viz. aromaticscontentandthetypeofotheroxygenatespresent.

Figure5EffectsofalcoholadditiontogasolineRVP(1psi=7kPa)
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Thefigure5istakenfromthewebsitedocumentUseofMethanolasaTransportation Fuel(Bechtold.,Goodman&Timbario)(2007))[12]. Measurement StandardtestasperEN228:2008EN130161 Thebasictestforthiskindofmeasurementissampleofairfuelmixtureistakenintheratio of 4:1 at 37.8oC. The mixture is then filled in a chilled chamber and connecting to air chamber which is in turn connected to pressure gauge. The apparatus is immersed in the waterat37.8oCandshakenperiodicallyuntilconstantpressureisreached. PurposeofmeasurementforRM3blend TotestforthevariationinvaporizationofRM3blends 3.2.2 Distillationcharacteristics Definition E70/E100/E150arethetemperatureregionswherecertainvolumeoffuelisevaporatedas showninthefigure7.At700C,100Cand1500Cthepercentagevolumeoffuelevaporatedis approximately25%,48%and88%respectivelyatatmosphericpressure.

Figure6Sampledistillationcharacteristicsofgasoline Thefigure6istakenfromwebsitedocumentPropertiesofpetrol(Anon.,(2005))[14]
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Referencespecifications Innr.560/2007standardspercentagevolumeofevaporation(In.Nr.560/2007)[13] x E100At1000Cminimumvolumeofevaporationshouldbe46%orabovebyvolume x E150At1500Cminimumvolumeofevaporationshouldbe75%orabovebyvolume ChangeinpropertyduetoRMblending

Figure7Effectofalcoholadditiontogasolinedistillation
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Thefigure7istakenfromthewebsitedocumentUseofMethanolasaTransportationFuel (Bechtold.,Goodman&Timbario)(2007))[12] The figure 7 shows the effect of blending alcohol to the gasoline distillation. It can be seen that the methanol has highest distortion effect on the distillation curve while the higher alcohols has lesser effect. This is due to methanol forming azeotropic mixtures with some elementsofgasoline. However, the above figure is for 15% blend of methanol into gasoline while CRIs final productisonlya3%blendandwoulddistortthecurvetoasmallextent. Measurement StandardtestasperEN228:2008ENISO3405 The basic experiment to measure the percentage volume of the fuel evaporation at the certaintemperatureandatatmosphericpressurecanbemeasured.Inthisexperimentfuel is taken in a container and heat is supplied to the container with varied temperatures at 1000C and 1500C. The container is connected to the tube which passes through the ice water bath to condense the vapour and eventually the fuel is collected in the measuring cylinder. PurposeofmeasurementforRMblend To determine the change in the evaporation of the RM3 blend at the specified temperatures. 3.3 STABILITYANDOTHERS
3.3.1 OxidationStability Definition Theabilityofthegasolinetoresisttheformationofgum,sludgeanddepositionduringlong termstorageduetooxidationiscalledoxidationstability. Referencespecification EN228:2008specificationmethodrequiresatleast360minutesofstorageoffuelsample withoxygenunderpressurewithoutforminganygum.(Anon.,(2008))[14].
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ChangeinpropertyduetoRMblending Alreadyexistingoxygencontentpresentingasolineduetomethanolcouldinhibitgum formationduringlongstorages.OxidationstabilityofRM3couldreducebuthoweverit couldbeinsignificantandmeetthereferencerequirements. Measurement SpecifiedtestforEN228:2008ENISO7536 Thetestmethodinvolvesinstorageofthegasolineinthepresenceofoxygenandthetime ismeasuredbeforetheoxygengetsabsorbedinthegasoline.(Anon.,(2008))[14]. PurposeofmeasurementforRMblend Toidentifyanyadditivesrequiredtolimittheoxidationrate 3.3.2 ResidueandExistentgumcontent Definition Residue is the percentage of volume remaining after the distillation end point is reached and represents the proportion of nonvolatile components in the fuel. This material, which isprimarilywaxesandgums,mayformdepositsinenginefuelenginesystems. The residue is then washed in a solvent before drying and weighing to determine the amountofgumpresentwhichistheexistentgumcontent.(Anon.,(2008))[14]. Referencespecification Residue:TheEN228specificationslimitthevolumeoftheresidueby2%byvolume. Existent gum content: Maximum allowable presence of existent gum is 5mg/100ml of fuel accordingtotheEN228specifications(Anon.,(2008))[14]. ChangeinpropertyduetoRMblending Residue:ThequantityoftheresidueinRM3blendmaybelowerthantheresiduefromthe basegasolinebecause3%ofthegasolineisreplacedbymethanolwhichhaslowerboiling pointthanfinalboilingpointofgasoline.
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Existentgumcontent:Gumformationmightoccuringasolineinpresenceofmethanoldue totheincreasedoxygencontentofmethanol.However,at3%RMingasolinenoeffectsare expectedonthegumcontent. Measurement Residue:SpecifiedtestforEN228:2008ENISO3405 Existentgumcontent:SpecifiedtestforEN228:2008ENISO6246 PurposeofmeasurementforRMblend ToidentifyifanyadditivesarerequiredtobeaddedtotheRM3blendtoinhibitthegum formationinthefuel. 3.3.3 CopperStripCorrosion Definition Thecorrosivenessofthegasolinetocoppercontainingpartsofthevehiclesfuelsystemis examinedbythecopperstripcorrosiontest. Referencespecification Copperstripcorrosiontestrequirestheratingclass1,at500Cfor3hrs.(Anon.,(2008))[15]. ChangeinpropertyduetoRMblending RateofcorrosivenessisexpectedtoincreaseintheRM3blendduetoincreasedoxygen contentbymethanoladdition.However,at3%RMingasolinenoeffectsareexpectedin corrosionduetotheRM3blend. Measurement SpecifiedtestforEN228:2008ENISO2160 Astripofcopperisimmersedinthesampleoffuelforadefinitetimeandataconstant temperaturethentocomparethestripwiththecolourstocalibratetherateofthe corrosion. PurposeofmeasurementforRMblend
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Todeterminetheclassofcorrosionandtoidentifyifanyrequiredadditivesarerequiredto stallthecorrosion 3.3.4 FinalBoilingPoint(FBP) Definition FinalBoilingPointisatemperatureatwhichthelastdropletevaporatesinthedistillationof gasoline. Referencespecifications TheEN228specificationgivesthefinalboilingtemperatureatmaximum2100C.(Anon., (2008))[14]. ChangeinpropertyduetoRMblending PossibleriseinFBPcouldindicateformationofgumandincreasedresidueduetooxygen contentofmethanolpresentingasoline.However,at3%ofRMblendedingasolinethe finalboilingpointisnotexpectedtochange. Measurement StandardtestasperEN228:2008ENISO3405 PurposeofmeasurementforRM3blend TodeterminethechangeinthefinalboilingpointduetothemixtureformedbyEN228 standards. 3.4 PHASESTABILITY
Water present in the RM blend could separate gasoline and methanol due to the polarity differences between the water and the fuel. This could lead to increase corrosion due to methanolwatermixturesseparatingoutinthefuelsystemsandcausecorrosion.Tolerance of gasoline methanol blends to the water also depends upon the base gasoline specificationsasshownintable4:
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Table4Methanolsolubilitybasedongasolinecomposition
Thetable4istakenfromthedocumentUseofMethanolasaTransportationFuel (Bechtold.Goodman&Timbario)(2007))[12]. Further water tolerance of gasoline methanol blends also depends on the amount of methanol blended to gasoline for temperatures higher than 8oC (45oF) it is observed that with the increase inmethanol content in gasoline the water tolerance increases (see figure 8). However, for temperatures less than 8oC the water tolerance decreases with the increasedmethanolcontent. Based on the above information an RM3 blend would have better phase stability at lower temperatures and possibility of better phase stability at higher temperatures based on the basegasolinecompositions. In general the base gasoline contains 0.0012 % w/w of water. CRIs RM consists less than 0.1% w/w water, which corresponds to 0.003% for the total RM3 blend. Thus the RM3 blendisexpectedtohave0.0042%w/wwater.
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Figure8Watertoleranceofgasolinemethanolblends(330%meoh)
Thefigure8istakenfromthedocumentUseofMethanolasaTransportationFuel (Bechtold.,Goodman&Timbario)(2007))[12]. ToensurephasestabilityoftheRM3blenditisnecessarytoperformthefollowingtests: 1. Measurementofwatercontent 2. Phaseseparationoftheblendatroomtemperaturebyaddingwater 3. Phaseseparationoftheblendat30oC The above requirements to ensure phase stability are references from Chinese methanol gasolineblendstandardsasimplementedinShanxiprovince.(Anon.,(2008))[16]. 3.4.1 Watercontent Definition TestforthewatercontentintheRM3blend. ChangeinpropertyduetoRMblending NoincreasedpresenceofwaterisexpectedintheRM3blendbecauseCRIsRMconsistsof lessthan0.1%w/wwater,whichcorrespondsto0.003%forthetotalRM3blendwhichis negligible. 36 OptimizationoflowvolumeRenewableMethanolblending
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Measurement StandardKarlFischertitration PurposeofmeasurementforRMblend Todetermineanywaterpresentinthemethanolgasolineblend. 1. Phaseseparationbyadditionofwateratroomtemperature(Anon.,(2008))[16]. Definition Experiment for phase separation by addition of 0.2% w/w (0.15% v/v) of water to RM3 blend. ChangeinpropertyduetoRMblending Phase separation may occur at 3% RM blending into gasoline when 0.2% w/w water is added to RM3 blend at room temperature (25oC/77oF). However, phase separation also depends on the base gasoline specifications, which may improve phase stability in specific cases. Measurement Measurementismadebyvisualinspectionofphaseseparation. PurposeofmeasurementforRMblend Testforthephaseseparationintheblendfuel. 3.4.2 Phasestabilityat300C Definition PhasestabilitytestontheRMblendfuelat300C(Anon.,(2008))[16]. ChangeinpropertyduetoRMblending Phase separation may not occur at30oC as RM3 blend has better water tolerance (0.04% w/w)thanhighermethanolblends.However,phaseseparationalsodependsuponthebase gasoline specifications and the amount of water present in the base gasoline itself. If the
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base gasoline is ensured to have very low water content, less than 0.04% w/w, phase separationmaynotoccur. Measurement Measurementismadebyvisualinspectionofphaseseparation. PurposeofmeasurementforRMblend Todetermineoccurrenceofanyphaseseparationat300C. 3.5 SUMMARY All the properties of the gasoline methanol blends that are subjected to change and need experimentation for measurements are studied. While some of the properties are legal requirementsCRIisinterestedinunderstandingsomemorepropertiesforitsmarketentry. It is understood that addition of RM to gasoline would have a positive effect on Octane Number and thus it is identified that it is not necessary for measurement through experimentationforthescopeofthisstudy. Adding RM to gasoline has the highest effect on the volatility properties of the final RM3 blend. Especially, RVP of the RM3 blend is expected to rise up to 35% from its base gasoline. At 3% RM blending into gasoline the distillation characteristics are not expected tochangemuch. There would be an increase in the oxygen content of the RM3 blend because of the methanol addition. In general increased oxygen content in the fuel is expected to decrease the stabilityof the fuel.However, at 3% low level blendingof RM into gasoline thestability ofRM3isexpectedtobewithintherequirements. Due to the polar differences between the gasoline and methanol, presence of water in the low volume methanol blended gasoline could cause phase separation, leading to problems in the vehicle performance. It is in general expected that RM3 blend would have 0.0042% w/w water under normal conditions of RM and gasoline blending under these conditions phase separation is not expected to happen either at normal and low temperatures. Also RM3 blend has better phase stability at lower temperatures. However, care needs to be
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taken to ensure no water addition to the RM3 blend during the logistics to help improve thephasestability.
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4 DEVELOPMENTOFTHEBLENDTESTFACILITYATCRI
CRI decided to develop a blend testing laboratory to perform tests on the RM3 blend properties mentioned in section 3. For development of the blend test facility, standardized test methods and equipment were identified. CRI also decided to use an external laboratory, Fjolver, for some of the tests as necessary. The table 6 shows the required test standards for the RM3 blend properties measurement and the concerned test facilities for theexperimentstobeconductedwithinthescopeofthecurrentresearch.
Table5Requirementandtestmethodsforunleadedpetrol
Volatility OctaneNumber Volatility ReidVapourPressure Distillationcharacteristics StabilityandOthers Oxidationstability Residue Existentgumcontent Copperstripcorrosion FinalBoilingPoint Phasestability Watercontent Phasestabilityatroom temperature Phasestabilityat30C
MeasurementStandards EN130161:2007 ENISO3405:2000 ENISO7536:1996 ENISO3405:2000 ENISO6246:1998 ENISO2160:1998 ENISO3405:2000 KarlFischertitration ReferenceofShanxi Province ReferenceofShanxi Province
Testfacility Testnotrequired CRI CRI CRI Fjolver Fjolver CRI CRI CRI CRI

Thedataintable5formeasurementstandardsaretaken(Anon.,(2008))[14]and(Anon., (2008))[16].
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Table6TeststandardsforRM3blendpropertiesmeasurement
Standardno. EN130161 ENISO3405 ENISO7536
Title Determinationofairsaturatedvapourpressure(ASVP)and calculateddryvapourpressureequivalent(DVPE) Petroleumproducts Determinationofdistillationcharacteristicsat atmosphericpressure Methodsoftestforpetroleumanditsproducts.Petroleum products.Determinationofoxidationstabilityofgasoline.Induction periodmethod Petroleumproducts Gumcontentoflightandmiddledistillate fuelsJetevaporationmethod Petroleumproducts CorrosivenesstocopperCopperstriptest
ENISO6246 ENISO2160
Thedataintable6istakenfromprintdocumentAutomotivefuelsUnleadedpetrol Requirementandtestmethods(Anon.,(2008))[14]. 4.1 ESTABLISHMENTOFBLENDTESTFACILITY
Required equipment, which complies with the European standardized method of testing, waspurchasedbyCRIfortheblendtestingfacility.Setupandinstallationoftheequipment wasdoneaccordingtothemanufacturersmanual.Initialexperimentswereconducted,for qualitypurposes,todeterminetherepeatabilityandprecisionoftheequipment. 4.1.1 RVPtestfacility The Vapour Pressure Tester is a benchtop automatic instrument for measuring the vapour pressureofgasoline,solvents,lightcrudeoilandsimilarproducts.Atwolinedigitaldisplay instructs the operator through the test sequence and displays the test result and status information. The end point of the test is determined automatically according to the prescribed Test Method. All valve operations are automated and use solventresistant Kalrezseals.
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Figure9RVPtestfacility
4.1.2 Distillationcharacteristicstestfacility Distillationunitconsistsofaheatingcoiloverwhichthedistillationflaskisplaced.Theneck of the distillation flask is connected to a tube which passes through a cooling bath (temperature01oC).Thedistillationflaskisfilledwiththefuelandheated.Theevaporated vapourpassesthroughthecoolingbathanddistillateiscollectedinagraduatedcylinder.
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Figure10Distillationcharacteristicstestfacility
4.1.3 Watercontenttestfacility The water content test facility is a titrator and of Aquamax KF model. It is easy to use, and supplied complete with a specifically designed low drift cell which is also suitable for outdoor use. CouLo Formula reagents have been specially formulated for use with Aquamax KF titrators. Formula A anode reagent is suitable for most routine applications and is especially useful for water content determination of oil samples, e.g. transformer oils,crudeoils,etc. Karl Fischer titration is simply a means to measure water content of samples. Modern instruments, such as the Aquamax, use the coulometric principle, whereby the water presentinthesampleiscoulometricallytitratedtoapredefinedendpointatwhichthereis aminuteexcessoffreeiodinepresent.Stoichiometrically,1moleofwaterwillreactwith1 mole of iodine, so that 1 milligram of water is equivalent to 1071 coulombs of electricity. Combining the coulometric technique with Karl Fischer titration, Aquamax titrators determine the water content of the sample by measuring the amount of electrolysis currentnecessarytoproducetherequirediodine.Thisisanabsolutetechniquewhichdoes notrequirecalibrationofthereagents.
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Figure11Watercontenttestfacility
4.1.4 Coolingfacility ThiscoolingfacilityisusedtotestthephasestabilityoftheRMblendsatlowtemperatures. In the cooling facility, required temperature can be attained by varying mixture of acetone and dry ice. Samples are taken in the test tubes, attached with a thermometer, and are partiallyimmersedintotheacetoneanddryicemixtureandallowedtocool.Phasestability ismeasuredbyvisualinspectionofthesampleoncetherequiredtemperatureisattained.

Figure12Coolingfacility
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4.2
QUALITYASSURANCEREPEATABILITY
4.2.1 RepeatabilitytestforReidVapourPressureequipment Under the category of volatility repeatability tests were conducted on vapour pressure equipment to determine repeatability of results as per the standards for Reid Vapour Pressure measurements. Twenty tests were conducted with pentane. The results are as followsintable7:
Table7Repeatabilitytestresultsofvapourpressureequipment

Samplenumber (container) 1(1) 2(1) 3(1) 4(1) 5(1) 6(1) 7(2) 8(2) 9(2) 10(2) 11(2) 12(2) 13(2) 14(2) 15(2) 16(3) 17(3) 18(3) 19(3) 20(3)
DryVapour Pressure Equivalent(kPa) 104.8 104.3 105.8 105.9 106 106.2 106 106.2 105.7 105.4 105.3 105.4 105.7 104.8 106.2 105.4 103.9 104.7 105.4 106
Precision acceptability range according to the European standards is 103.9 106.3 kPa for pentane. Obtained test results as above range from 103.9 106.2 kPa. Thus, it can be
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concluded that the equipment fulfils the repeatability criteria according to European standards. 4.2.2 Repeatabilitytestresultsfordistillationcharacteristicsequipment Repeatability tests were conducted on summer gasoline for determination of the repeatability of the distillation characteristics equipment. The operating procedures of the equipment require the operator to manually control the heat input to the distillation flask toensureacertainquantityofdistillateisformedatagivenrate(say1mlinapproximately 1 minute). This induces an inherent repeatability error of performing the experiment as a rateofheatinputprovidedfordifferentsampleswouldnotbeexactlythesame. Repeatability results are shown in table 8. It can be observed that the repeatability range fromthetestsdidnotmatchthecriteriafortherepeatabilitygiveninthestandards.Thisis mainly due to the manual operation of equipment as mentioned above. The repeatability range measured shall be used as a benchmark for all the calculations in this study against therequiredspecifications.
Table8Repeatabilityresultsfordistillationcharacteristics
Percentagerecovered %vol IBP 5 10 20 30 40 50 60 70 80 90 95 FBP
Requiredrangefor repeatability,oC 3.30 2.74 2.08 2.08 1.90 1.90 1.90 1.90 1.90 1.50 2.94 1.50 3.90
Rangefromthe repeatabilitytests, o C 6.00 11.65 11.64 10.15 9.15 6.36 6.28 8.11 5.42 9.03 8.70 12.87 10.00
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4.3
SUMMARY
The lab facility for RM3blend testing was developed at CRIfor volatility and phase stability tests. External lab facility of Fjolver shall be used for testing of RM3 fuel stability and others. The equipment was purchased and set up according to instruction manuals from the manufacturer. Experimental procedures were developed based on the European standards. Quality assurance tests were performed for vapour pressure and distillation characteristics test facilities. The vapour pressure equipment met with the repeatability criteria. The distillation characteristics equipment could not meet the repeatability criteria due to the nonrepeatability of the manual control of heating. However, the range of repeatabilitydataobtainedisusedasabenchmarkfortherepeatabilityresultsinfuture.
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5 RM3BLENDTESTINGEXPERIMENTSANDRESULTS
To perform the RM blend testing, Olis 1 supplied CRI with summer and winter gasoline in sealed containers. Samples of RM3 were made using this base gasoline and RM produced fromCRIspilotscaleRMproductionfacility. 5.1 RESULTSFORREIDVAPOURPRESSURE(RVP)
5.1.1 SummerbasegasolineandsummerRM3 Blending of 3% RM in summer base gasoline increased Reid Vapour Pressure from 67.13 kPato80.93kPa.TheresultsforsummerbasegasolineandsummerRM3forRVPareshown intable9and10.
Table9RVPresultsforsummerbasegasoline
S.No 1 2 3 Average StandardDeviation

Sample Basegasoline Basegasoline Basegasoline
RVP inkPa 67.00 67.10 67.30 67.13 0.15
Table10RVPresultsforsummerRM3
Sample RM3 RM3 RM3
RVPinkPa 80.70 81.40 80.70 80.93 0.40

1
OlisisoneofthelargestimportersofgasolineinIceland.www.olis.is
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Figure13RVPofbasegasoline&RM3(summer)
5.1.2 WinterbasegasolineandwinterRM3 Blending of 3% RM in winter base gasoline increased Reid Vapour Pressure from 86.57 kPa to 102.10 kPa.The results for winter base gasoline and winter RM3 for RVP are shown in table11and12.
Table11RVPresultsforwinterbasegasoline

Sample Basegasoline Basegasoline Basegasoline
RVPinkPa 86.60 86.60 86.50 86.57 0.06

Table12RVPresultsforwinterRM3

Sample RM3 RM3 RM3
RVPinkPa 101.80 102.10 102.40 102.10 0.30
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Figure14RVPofbasegasoline&RM3(winter)
5.1.3 DiscussionforVapourPressure Vapour pressure of the summer RM3 blend was 20% higher than the base gasoline and exceeded the legal requirements of 70 kPa by 10 kPa. A similar rise in the vapour pressure isobservedinthewinterRM3blendbuttherearenolegalrequirementspresent.Thus,the RM3 blend is acceptable during the periods of winter (9 months a year other than July, AugustandSeptember). 5.2 RESULTSFORDISTILLATIONCHARACTERISTICS As discussed in previous sections E100 and E150 of gasoline fuel are regulated by Icelandic legislation,whileCRIisinterestedintheFinalBoilingPoint.Furtheroveralldistillationcurve of a fuel explains the effect of volatility on the vehicle driveability. Thus, the complete distillationcurvesweredrawnforbothgasolineandtheRM3blendforacomparison. 5.2.1 Resultsfordistillationcharacteristicsofbasegasoline(summer) Themaindistillationcharacteristicsforsummergasolinewerecalculatedandcrosschecked withthereferencespecificationsasshownintable13.
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Table13Resultsfordistillationcharacteristicsofgasoline(summer)
Description Sampleno.1 Sampleno.2 Averageof1and2 Referencespecification
E100(in%) 51 51 51 46(min.)
E150(in%) 87 88 87.50 75(min.)
FBP(in0C) 185 184 184.50 210(max.)
5.2.2 ResultsfordistillationcharacteristicsofRM3(summer) The main distillation characteristics for summer RM3 were calculated and cross checked withthereferencespecificationsasshownintable14.
Table14ResultsfordistillationcharacteristicsofRM3(summer)
E100(in%) 56.95 55.95 56.45 46(min.)
E150(in%) 89.55 89.95 89.75 75(min.)
FBP(in0C) 186 183 184.50 210(max.)
5.2.3 DistillationcurveofbasegasolineVsRM3 TheoveralldistillationcurveofbasegasolineiscomparedwiththatofRM3scurveinfigure 15.
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Temperature(C)
Basegasoline RM3
Distillate(in%)
Figure15DistillationcurveofbasegasolineVsRM3(summer)
5.2.4 Resultsfordistillationcharacteristicsofbasegasoline(winter) The main distillation characteristics for winter gasoline were calculated and cross checked withthereferencespecificationsasshownintable16.
Table15Resultsfordistillationcharacteristicsofbasegasoline(winter)

E100(in%) 51.88 51.90 51.89 46(min.)
E150(in%) 84.88 83.90 84.39 75(min.)
FBP(in0C) 186 195 190.50 210(max.)
5.2.5 ResultsfordistillationcharacteristicsofRM3(winter) ThemaindistillationcharacteristicsforwinterRM3werecalculatedandcrosscheckedwith thereferencespecificationsasshownintable16:
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Table16ResultsforthedistillationcharacteristicsofRM3(winter)
E100(in%) 53.03 53.06 53.05 46(min.)
E150(in%) 85.03 85.06 85.05 75(min.)
FBP(in0C) 192.5 193 192.75 210(max.)
5.2.6 DistillationcurveofbasegasolineVsRM3(winter) The overall distillation curve of base gasoline is compared with that of RM3s curve below infigure16:
Temperature(C)
Basegasoline RM3
Distillate(in%)

Figure16DistillationcurveofbasegasolineandRM3(winter)
5.2.7 Discussionfordistillationcharacteristics The E100 and E150 values of both summer and winter RM3 blends increased from that of corresponding base gasoline. The legislation specifies a minimum requirement on both E100 and E150. Thus, there shall be no problem in the acceptability of RM3 blends for distillationcharacteristics. 5.3 RESULTSFORSTABILITYANDOTHERS
Theobtainedresultforcopperstripcorrosiontestfollows: OptimizationoflowvolumeRenewableMethanolblending
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Table17Resultforcopperstripcorrosionforsummerandwinter
Sample RM3
Result Class1A
EN228standards Class1(required)
5.3.1 Resultforexistentgumcontent Theobtainedresultforexistentgumcontenttestfollows:

Table18Resultforexistentgumcontentforsummerandwinter
Sample RM3
Result,mg/100ml <1
EN228standards,mg/100ml 5(max.)
5.3.2 Resultforresidue Theobtainedresultforexistentgumcontenttestfollows:

Table19Resultforexistentgumcontentforsummerandwinter
Sample RM3
Result,%V/V 1
EN228standards,%V/V 2(max.)
5.3.3 Discussionforstabilityandothers As it can be seen from the results obtained for both summer and winter RM3 blends are complied with all the requirements for copper strip corrosion, residue, existent gum content and final boiling point. Oxidation stability test is currently not performed due to nonavailabilityoftheequipmenteitheratCRIoratFjolver.
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5.4
RESULTSFORPHASESTABILITY
Tests were conducted for summer and winter RM3 to determine the phase stability of the blends. In this test, samples of summer and winter RM3 were prepared from the obtained gasoline.Testsareconductedintwosteps. 1. Testforphaseseparationatroomtemperaturewithvaryingwatercontent Samplesweretestedforphasestabilityatroomtemperaturewithincreaseinwater contentintheblends.Thephaseseparationtestforroomtemperatureistocheckif the RM3 blend phase separates with addition of 0.2 % w/w water. In the current test water is added in small quantities and the water content of the RM3 blend is measured and check for phase separation in stages due to the difficulty of addition of water manually, it is difficult to control the actual steps of quantity of water addedtotheRM3blend. 2. Testforphasestabilityat300C Samples were placed incooling facility to reduce the temperature to300C to check forphaseseparationoftheblends.
Table20PhaseseparationresultsforsummerRM3atroomtemperature
Sample RM3 RM3 RM3 RM3 RM3 RM3
Watercontent% (w/w) 0.0309 0.0310 0.0376 0.0379 0.0399 0.0384 0.0450 0.0436 0.0520 0.0532 0.1700 0.1640
Temperature(0C) roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature
Result Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation Phaseseparation Phaseseparation
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Table21PhaseseparationresultsforsummerRM3at300C
Sample RM3 RM3 RM3
Watercontent%(w/w) 0.0207 0.0267 0.0267
Temperature(0C) 30 30 30
Result Nophaseseparation Nophaseseparation Nophaseseparation
Table22PhaseseparationresultsforwinterRM3atroomtemperature
Sample RM3 RM3 RM3
Watercontent% (w/w) 0.0378 0.0346 0.0519 0.0543 0.0779 0.0723
Temperature(0C) roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature

Result Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation phaseseparation phaseseparation
Table23PhaseseparationresultsforwinterRM3at300C
Sample RM3 RM3 RM3
Watercontent% (w/w) 0.0251 0.0253 0.0253
Temperature(0C) 30 30 30
Result Nophaseseparation Nophaseseparation Nophaseseparation
Water content of the normal RM3 blend as measured was less than 0.03. From the test results for phase stability in the above table 21 and table 23 it can be seen that there was no visible phase separation of summer and winter RM3 samples at 300C with this water content. The summer RM3 did not phase separate at water content of 0.053% w/w water which is double the amount of water present in summer RM3 as such. The winter RM3 also did not phase separate at water content of 0.054% w/w water which is double the amount of water present in winter RM3 as such. The phase separation of summer RM3 and winter 56 OptimizationoflowvolumeRenewableMethanolblending
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RM3occurredatwatercontentsof0.167and0.072%(w/w)respectively.Phaseseparation at intermediate water content levels could not be tested due to the difficulty of water addition. This shows that at room temperature condition the water content of RM3 blend shouldnotincreasemorethan~0.055%w/wtoensurephasestability. 5.4.1 DiscussionforPhasestability As can be seen from the obtained test results obtained for both summer and winter RM3 blends for phase stability that the phase separation does not occur at 300C. At room temperature phase stability of the RM3 blends is maintained as long as the water content oftheblendsdoesnotexceed~0.055%w/w. 5.5 SUMMARYOFRESULTS
All the results of the experiments along with some other calculated properties of both summer and winter RM3 are presented below table 24 and 25. These properties of RM3 can be compared with either the legislative requirements (first column in blue) or the reference specifications (first column in black). The acceptability of the blend for a specific propertyisyes(y)iftheRM3propertymeetsthenecessaryspecificationsorno(n)ifitdoes not.

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Table24compilationofresultsforsummerRM3
Property
ResearchOctaneNumber MotorOctaneNumber ReidVapourpressure,summer period Distillation: Percentageevaporatedat100 C Percentageevaporatedat150 C Hydrocarbonanalysis Olefins Aromatics Benzene Oxygencontent Oxygenates Methanol Ethanol isoprpylalcohol tertbutylalcohol isobutylalcohol ethers(C5+) otheroxygenates Sulphurcontent Leadcontent OxidationStability Copperstripcorrosion Existentgumcontent Residue FinalBoilingpoint Phasestabilityatroomtemperature Phasestabilityatlowtemperature
o o
Units
kPa %V/V %V/V %V/V %V/V %V/V %m/m %V/V %V/V %V/V %V/V %V/V %V/V %V/V Mg/kg g/l minutes Mg/100 ml %V/V
o
Limits
Min 95 85 46 75 360
SummerBase gasoline
Max 70 18 35 1 2.7 3 5 10 7 10 15 10 10 0.005 Class 1 5 2 210 95.6 86.6 67.6 54.7 89.9 3.4 31 0.44 2.04 11.31 6.6 <0.005 360 Class1A 1 1 184.5
Summer RM3
95.6+ 86.6+ 80.93 56.45 89.75 3.3 30 0.43 3.48 3 10.97 6.4 <0.005 NA Class1A 1.4 1 184.5
Acceptability
Y Y N Y Y Y Y Y Y2 Y Y Y Y Y Y Y Y Y Y Y Y Y Y y3 Y
C

2
Yesbasedonfuturelegislationchangesbasedon2009/28/ECimplementationinIceland,whereoxygen contentisasallowedupto3.7%m/m Watercontenttobelessthan~0.055%w/w
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Table25ResultsforwinterRM3(EN228specifications)
Property
Units
Limits
Winter Base gasoline Max

18 35 1 2.7 3 5 10 7 10 15 10 10 0.005 Class1 5 2 210 95.1 85.2 86.57 51.89 84.39 11.1 29.8 0.58 <0.05 <0.05 8.5 <0.005 360 Class1A 1 1 190.5
Winter Acceptability RM3

95.1+ 85.2+ 102.1 53.05 85.05 10.8 28.9 0.56 1.5 3 <0.05 8.2 <0.005 NA Class1A <1 1 192.75 Y Y y y y y y y y y Y Y Y Y Y Y Y Y Y Y Y Y Y y4 Y

ResearchOctaneNumber MotorOctaneNumber ReidVapourpressure,winterperiod Distillation: Percentageevaporatedat100 C Percentageevaporatedat150oC Hydrocarbonanalysis Olefins Aromatics Benzene Oxygencontent Oxygenates Methanol Ethanol isoprpylalcohol tertbutylalcohol isobutylalcohol ethers(C5+) otheroxygenates Sulphurcontent Leadcontent OxidationStability Copperstripcorrosion Existentgumcontent Residue FinalBoilingpoint Phasestabilityatroomtemperature Phasestabilityatlowtemperature
o
Min
kPa %V/V %V/V %V/V %V/V %V/V %m/m %V/V %V/V %V/V %V/V %V/V %V/V %V/V Mg/kg g/l minutes Mg/100 ml %V/V
o
95 85 46 75 360
C

4
Watercontenttobelessthan~0.055%w/w
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5.5.1 Otherlegalrequirements The legislation specifies a maximum requirement on each of aromatics, olefins, benzene, oxygenates, sulphur and lead. As it can be seen from above table by addition of RM the values of these properties in the final RM3 blend decrease from the base gasoline, thus supporting the legal requirements in all cases assuming that the base gasoline meets the specifications. The oxygen content rises in the RM3 blend from the base gasoline and as seen in the case of summer RM3 blend it went up to 3.48 % m/m while the maximum requirement is only 2.7 % m/m. However, the new EU directive 2009/28/EC shall be implemented soon in Iceland which would mandate the maximum requirement of 3.7 % m/m on the oxygen content.Thus,bothsummerandwinterRM3blendsareacceptableforoxygencontent. 5.6 SUMMARY
Base gasoline was obtained from Olis and RM3 blend tests were performed for both summer and winter RM3 blends. Test results were analyzed and compared for the acceptability of legislation and other reference specifications. The two main conclusions fromthetestsare 1. WinterRM3blendcomplieswithallthelegislationandreferencespecifications. 2. Summer RM3 blend complies with all but one of the specificationsReid Vapour Pressure.
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6 RM3BLENDOPTIMIZATION
In the previous chapter from the obtained test results it was found that one of the properties for the summer RM3 blend, Reid vapour Pressure, did not meet the legislation specifications.Inthischapterweshallbediscussingthepossibletechnicalsolutionsandthe test results to reduce the RM3 blend RVP to the required legislation specifications. Based ontheliteraturestudiesthefollowingmethodsarepossibletoobtainan RM3blendwitha controlledRVP: 1. Additionofcosolvents 2. LowvapourPressurebasegasoline 6.1 ADDITIONOFCOSOLVENTSFORRVPREDUCTIONSECONDARYRESEARCH
The presence of methanol has a dramatic effect on the RVP of the gasoline to which it is added. However, with addition of higher alcohols the effect of methanol on RVP is decreased to an extent as methanol will be able to bond with the higher alcohols and thus reducingthevapourpressure.Ethanol,propanolsandbutanolsarehigheralcoholsthatcan beblendedintogasolineaccordingtothecurrentlegislationandthuscanbeutilizedasco solvents.(Bechtold,R.L.,Goodman,M.B.,&Timbario,T.A.(2007))[12] Due to the difference in availability of cosolvents in terms of quantity and cost and possible differences in the effects of RVP on RM3 blend, it is decided to obtain cosolvents andtesttheRM3blendswithRVP.Thecosolventsselectedforperformingthetestsare: 1. 2. 3. 4. 5. 6.2 Ethanol 1Propanol 2Propanol 1Butanol Tertiarybutylalcohol RVPTESTSWITHCOSOLVENTSFORSUMMERRM3BLENDRESULTS
Cosolvents selected were obtained in container and RM3 blend samples were prepared with addition of these cosolvents with varying volumes (15%) in steps of 1%. Three tests were performed for each of the sample and the results were averaged. The results for the RVP of summer RM3 blend with these various cosolvents with varying volumes are shown infigure17,18,19,20,21.
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6.2.1 RM3blendwithEthanolascosolvent Byadding3%ofRMinbasegasolinetheRVPoftheRM3blendrosefrom67kPato81kPa, while the legislative requirement is 70 kPa. When ethanol was used as a cosolvent with RM3 blend, it is observed that initially (1% ethanol) there was minor increase in the RVP, butwithfurtherincreaseinvolumeofethanolinRM3blend,theRVPreduced. The initial increase could be attributed to the fact that ethanol itself in general contributes toRVPingasolineandasethanolconcentrationincreasesthecosolventeffectcanbeseen moreclearly.ThereductioninRVPfromRM3toRM3+5%ethanolblendisonly3kPa.The RM3 blend with ethanol up to 5% ethanol would not be able to meet the target RVP of 70 kPa.

Figure17RVPresultsforRM3blend+(15%)ofethanol
6.2.2 RM3blendwith1Propanolascosolvent When 1Propanol was added to the RM blend initially (1%) it did not contribute for the reduction of RVP in the RM3 blend but with further increase in the concentration of 1 Propanol there was a visible decrease in RVP. 3% of this cosolvent only contributed to a decrease of 4 kPa in RVP bringing the RM3 blends RVP from 81 kPa to 77 kPa. The RM3 blend with 1Propanol at the above mentioned volume levels could not reduce the RVP to thetargetRVPof70kPa.
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Figure18RVPresultsforRM3blend+(13%)of1Propanol
6.2.3 RM3blendwith2Propanolascosolvent Adding 2Propanol to the RM3 blend showed the similar trends of decrease in RVP like 1 Propanol. 3% of this cosolvent only contributed to a decrease of 3.3 kPa in RVP bringing theRM3blendsRVPfrom81kPato77.7kPa.TheRM3blendwith2Propanolattheabove mentionedvolumelevelscouldnotreducetheRVPtothetargetRVPof70kPa.

Figure19RVPresultsforRM3blend+(13%)of2Propanol
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6.2.4 RM3blendwith1Butanolascosolvent Varying volumes (15%) of 1 butanol was used as a cosolvent with RM3 blend. It was observed that initially by (1%) of cosolvent reduced the RVP of the RM blend but at (2%) the RVP of the blend increased to similar with RVP of RM3. However, with the increased concentration from (35%) there was a reduction in the RVP to 76 kPa at 5% blending, which is only 5 kPa. 1Butanol as a cosolvent could not reduce to the RVP of the blend to thetarget70kPa.

Figure20RVPresultsforRM3blend+(15%)of1Butanol
6.2.5 RM3blendwithTBAascosolvent Finally, TBA was used as a cosolvent with RM3 blend. It was observed initially that (1%) of cosolvent increased the RVP of the RM blend, but at (23%) concentration of TBA there wasareductioninRVP oftheblend.However,TBAasacosolventreducedtheRVPofthe RM blend by only 4 kPa at 3% blending. TBA could not reduce RVP of the blend to the target70kPa.
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Figure21RVPresultsforRM3blend+(13%)ofTBA
6.2.6 Discussionandconclusion AsseenfromthetestresultsaboveallthefivecosolventstestedwithRM3blendcouldnot help to bring back the RVP of the blend to target 70 kPa. At 3% blending of the cosolvents the reduced RVP levels are shown below. 1Propanol and TBA are identified to be the co solventswithbestRVPreductionontheRM3blendwhenblendedat3%.
Table26ResultsforsummerRM3withcosolvents Fuelblend Summerbasegasoline SummerRM3 SummerRM3+3%Ethanol SummerRM3+3%1Propanol SummerRM3+3%2Propanol SummerRM3+3%1Butanol SummerRM3+3%TBA RVP 67.13 80.93 79.56 76.93 77.70 79.10 77.00
Fromtheobtainedtestresultsasshownintable26thatbyaddingcosolventstosummer RM3,ItcouldbeseenthatRVPcouldbereducedbyaddingcosolventsbuttheRVPofthe blendsdidnotreachthespecifiedlegislationrequirements. 6.3 RVPTESTSWITHCOSOLVENTSFORWINTERRM3BLENDRESULTS
RVP tests were conducted on winter RM3 blends with cosolvents similarly to the tests conductedintheprevioussectionforthesummergasolineasshownintable27.RVPofthe
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obtained winter base gasoline is 86.57 kPa and by adding 3% of RM, RVP of the RM3 blend reached to 102.1 kPa. Even though there is no legislation specification for RVP of winter RM3 blend, the tests were conducted for reference purposes. The obtained RVP results using the cosolvents followed a similar pattern to that of summer RM3 blend results. 1 Propanol was found to be much more effective than the other cosolvents at 3% blend levels.
Table27ResultsfortheRM3blendswithcosolventsforwintergasoline
Cosolvent 1% 2% 3%
Ethanol 103.73 101.83 100.00
1Propanol 103.55 101.57 97.03
2Propanol 103.27 102.50 101.37
1Butanol 101.80 99.73 98.07
TBA 103.93 102.57 101.00
6.4
LOWVAPOURPRESSUREBASEGASOLINESECONDARYRESEARCH
The RVP of the gasoline which was supplied and tested at CRI is 67 kPa and thus the final RM3blendsRVPwastestedtobe81kPa.Incasewherethebasegasolinehasmuchlower vapourpressuretheRM3blendcouldpossiblybemeetingtheRVPrequirementof70kPa. INTROMETprogramdevelopedvariousmethanolandmethanolethanolblendstomeetthe summer vapour pressure requirements. It is observed from INTROMETs data that a base gasolineofRVP59kPawouldensurethatthesummerRM3blendsRVPislessthan70kPa. Similar data was observed for a 3% methanol 3% ethanol blend. (Boding, Henrik. (2010))[17].
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Table28INTROMETsdataonRVP(inkPa)ofbasegasolineandfinalblends
Thetable28istakenfromtheobtainedtestresultsfromINTROMETprogram(Boding, Henrik.(2010))[17]. AccordingtotheEuropeanUnionstandards,inthetropicalclimatepartofEuropeanUnion the member states should sell the gasoline with a maximum RVP of 60 kPa in summer period. This gasoline when blended with RM at 3% could meet the RVP requirements in Iceland. Since this gasoline is widely available in the market. This low vapour pressure gasoline is currently not available to perform the RVP tests. However, it is recommended thatCRIshouldperformtheseteststoconfirmthesecondaryresearchdata. CRI could look into the option of obtaining this lower vapour pressure gasoline as its base gasolineduringsummerperiodsandsolvingtheproblemofsummerRM3blendsRVP. 6.5 SUMMARY
TwooptionswereidentifiedtopossiblyreducetheRVPoftheRM3blendtothetargetlevel of 70 kPa. First, RM3 blend was tested with five cosolvents (higher alcohols) for RVP reduction.At3%blendinglevelofcosolvents1PropanolandTBAwerefoundtobehaving the best reduction effect on the RM3 blend. However, this reduction is not sufficient to reach the target RVP. Second, low vapour pressure base gasoline could be obtained for RM3 blend to reach the RVP target and this understanding is confirmed by the secondary researchdataobtainedfromtheINTROMETprogram.
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7 RM3 BLEND EFFECTS ON ENGINE PERFORMANCE AND EMISSIONS

The blend testing results for RM3 concluded that winter RM3 meets the legislation specifications for gasoline fuel while summer gasoline could be optimized for the required specification. Further it is important to also study the effects of RM3 on vehicles to ensure thecompletenessofRM3acceptability. Historically methanol has been used as a transportation fuel for various advantages like increased octane number and low emissions. There are number of studies performed on methanol gasoline blends. It was understood from the literature that there was a steep increase in the interest of the methanol as a gasoline blend for fuel since the oil hike of 1970s. Reputed automobile manufacturers like Volkswagen have conducted research. (Bernhardt,1977)[18] Withtheincreasedinterestofusingbioethanolasagasolineblendinlate1990sandearly 2000thefocusshiftedfrommethanoltoethanol.However,theincreaseddemandofglobal energyrequirement,theoilpricerisein2007,Chinasinterestinimplementingmethanolas a fuel, development of renewable and biomethanol production processes sparked recent interest in using methanol as a gasoline blend along with ethanol. (Bechtold, R.L., Goodman,M.B.,&Timbario,T.A.(2007))[12],(Anon.,(n.d.))[7]. Thisrecentinterestincreasedtheresearchonmethanolasafuelandisbuiltuponprevious research. While the fundamentals of earlier research remain the same the new research data gives much more limelight on how methanol blends effect the existing vehicle and engine technology. Detailed literature study is thus performed to understand the fundamentalsofvehicleperformanceonmethanolgasolineblendsandcertainvehicletests areperformedtovalidatethedata.
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7.1
FUNDAMENTALSOFRMGASOLINEBLENDEFFECTSONENGINEPERFORMANCE LITERATURESTUDY
Figure22Variationofpowerandtorquewithvaryingenginespeedsformethanolandgasoline blends[19]
Figure22istakenfromtheresearcharticleProperties,performance,andemissionsof methanolgasolineblendsinasparkignitionengine(Qi,Liu,Zhang,&Bian,YZh.(2005)) [11] Figure 19 shows the test results for power and torque output using methanol gasoline blends. It can be seen that using methanol gasoline methanol blends as fuel there is a marginal reduction in the power and torque output compared to gasoline fuel, this is due to lower energy content of methanol. Hence, using 3% methanol blends in gasoline is expectedtohaveaminorreductioninpowerandtorqueoutput.However,usingmethanol gasoline blends improves the combustion process due to increased oxygen content and laminarflamepropagationresultingintheincreaseofengineefficiency. 7.2 RMGASOLNEBLENDEFFECTSONENGINETESTRESULTS
Engine tests were performed in a dynamometer test facility at Borgarholtsskoli. The test vehicle is a Mitsubishi Carisma 2000 with 1.6 liter engine. Tests for performance, power and torque with engine speed, are done for winter gasoline and winter RM3 blend and the resultsarecompared. 1. Performancetests a. PowerVsRPM b. TorqueVsRPM
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Figure23PowerandtorquewithenginespeedforgasolineandRM3
From the results obtained, shown in figure 23 it is observed that power and torque from engine for winter RM3 blend is less than that of gasoline for engine speeds less than 3600 RPM. At speeds above 3600 RPM the power and torque output from the engine matched for RM3 blend and gasoline. The highest decrease in the torque from gasoline for the RM3 blendwas~9%andoccurredataround1300RPM.Whilethehighestdecreaseinthepower from gasoline for the RM3 blend was ~8% and occurred at around 3020 RPM. Obtained resultshowssimilartrendaslearnedfromtheliteraturestudy. 7.3 RMGASOLINEBLENDEFFECTSONENGINEEMISSIONSLITERATURESTUDY
EuropeanUnionregulatestheemissionsfromthecarsthroughspecificEUnorms.For gasolineenginesthecurrentregulatedemissionsareNitrogenoxides(NOx),Total hydrocarbon(THC),Carbonmonoxide(CO)andparticulatematter(PM).Inthissection studyisdonetounderstandtheeffectsontheemissionsbycombustionofmethanol gasolineblendsinSparkIgnition(SI)engine.Theemissionsformethanolgasolineblends havebeenstudiedextensivelyintheliterature.(Boding,Henrik.(2010))[17].
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In figure 24, from literature it is observed that carbon monoxide (CO) emissions and hydrocarbon emissions (HC) from the combustion of methanol gasoline blends are lower than theemissions from the combustion of gasoline fuel. This is due to the oxygen content in the methanol which helps in the complete combustion of fuel in the engine. By adding methanolCOandHCemissionsarereduced. In figure 24 for Nitrogen oxides (NOx) emissions are formed inside the engine when nitrogen from air entering the engine reacts with oxygen under high pressure and temperature. With 3% addition of methanol into gasoline the NOx emissions decrease. Methanol gasoline blends burns at lower temperature than gasoline. Hence, reducing the NOxemissions.

Figure24CO,HCandNOxemissionsformethanolgasolineblends
Thefigure24istakenfromtheobtainedtestresultsfromINTROMETprogram(Boding, Henrik.(2010))[17].
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A recent study of methanol gasoline blends is of particular interest as it is a fleet testing of vehicles funded by Swedish energy agency and supported by Statoil. Two tests were performed for particulate matter emission on New European Driving Cycle (NEDC) at various methanol concentrations in gasoline and are averaged and presented. The PM10 emissiondecreasedwithincreasedmethanolconcentration.(Boding,Henrik.(2010))[17].

Figure25PM10emissionsformethanolgasolineblends
Thefigure25istakenfromtheobtainedtestresultsfromINTROMETprogram(Boding, Henrik.(2010))[17]. 7.4 RMGASOLINEBLENDEFFECTSONENGINEEMISSIONSTESTRESULTS
Emission tests are performed on the same vehicle as mentioned in section 7.2 at engine speeds, ~2500 and ~5000 RPM. At moderate engine speed of ~2500 RPM, the emissions from the combustion of RM3 and RM10 blends were very low than that of gasolines. The CO and HC emissions improved considerably by blending RM into gasoline. RM3 has a bettereffectonimprovingNOxemissionscomparedtoRM10.
Table29Emissionsat~2500RPM Sample Gasoline RM3 RM10 CO(%vol) 0.41 0.09 0.04 HC(ppm) 156 29 36 NOx(ppm) 156 68 141 A/Fratio 1.014 1.007 1.006
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Gasoline
RM3
RM10
Percentageemissionscomparedto gasoline

Figure196CO,HCandNOxemissionsat~2500RPMforgasoline,RM3andRM10
At higher engine speed of ~5000 RPM, the CO and HC emissions of the gasoline decreased and NOx emissions increased compared to lower engine speed. The HC emissions of RM3 andRM10arehighercomparedtogasolineatthehigherenginespeedsbutlowertothatof gasoline at lower engine speed. However, the NOx and CO emissions are considerably higherfortheRMblendsathigherenginespeeds.Thisincreaseinemissionsispossiblydue toincompletecombustionathigherenginetemperature. Further the emission tests at higher engine speed have different air fuel ratios and thus cannotbecompared.BoththeRMblendshavericherairfuelratioleadingtohigherCOand HC emissions. Further tests need to be conducted to ensure similar parameters of test for rightcomparison.
Table30Emissionsat~5000RPM Sample Gasoline RM3 RM10 CO(%vol) 0.06 0.99 1.96 HC(ppm) 42 67 86 NOx(ppm) 185 927 478 A/Fratio 1.005 0.984 0.954
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7.5
SUMMARY
In order to identify the effects of methanol gasoline blends on engine performance and emissions a literature study and tests were conducted. RM3 improves efficiency of the engine. The torque and power output of the engine decreases marginally at lower engine speedsandaresameathigherenginespeedsforRM3comparedtogasoline. RM3 has lower CO, HC and NOx emissions according to the literature compared to the gasoline. This understanding is validated by an experiment of engine testing conducted at ~2500 RPM. However, the tests performed at ~5000 RPM did not have consistent air fuel ratio and thus the results are not comparable. Further emission tests with detail design of experimentsarerecommended.
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8 RM3 BLEND EFFECTS ON VEHICLE DRIVEABILITY AND COMPATIBILITY

While the effects of RM3 blend on engine performance and emissions were studied earlier and generalized to an extent, the actual effect will depend on the vehicle, the composition of the base gasoline and also the ambient conditions. Addition of methanol to gasoline brings the blends towards the lean limit of the combustion due to the presence of oxygen in methanol and could affect the driveability. The distillation curve is categorized in three partssuchasfrontenddistillate(lowerhydrocarbons),midrangedistillate(mediumhydro carbons) and backend (higher hydro carbons). Each range has an affect on the driveability ofthevehicle 8.1 EFFECTSOFSUMMERRM3ONDRIVEABILITY
It can be seen from the figure 27 comparison of distillation curve of summer gasoline and RM3thattheevaporationofthesummerRM3blendsisgenerallyhigheranditcanbeseen profoundlybetweentemperaturesof60oC170oC.
Temperature(C)
Basegasoline RM3
Distillate(in%)
Figure27DistillationcurveofbasegasolineVsRM3(summer)
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ThepossibleeffectsofRM3blendsondriveabilityandenvironmentalimpactinIcelandare mentionedbelow: Front End: There is not much change in the distillation curve in the front end of the summer RM3 blend from the gasoline. Thus, no effects of cold start or hot driveability are expected. Further the general ambient temperatures in Iceland are quite low during summer and seldom reach 20oC. This means even though the RVP of summer RM3 blend, measuredat37.8oC,ishighertheactualevaporativeemissionsareexpectednottoincrease tothesameextentduetolowambienttemperatures. Midrange: Significant difference is observed in the RM3 distillation curve compared to base gasoline. The increased volatility in the midrange could affect the driveability during cold and humid weather by forming ice in carburettors in engines. However, the vehicle technology today shifted from carburettors to direct injection systems also the general weather conditions in Iceland are dry and cold and seldom humid. Thus, with the extent of variationindistillationcurveofRM3inmidrangenodriveabilityaffectsareexpected. Back end: There is indication in RM3 distillation back end curve towards poor long trip economy. However, the variation is quite small and as studied earlier the increase in efficiency in the engine due to methanol addition offsets the decrease in calorific value of theRM3blend.Thus,nofueleconomyeffectsareexpected. 8.2 EFFECTSOFWINTERRM3ONDRIVEABILITY
It can be seen from the comparison of distillation curve of winter gasoline and RM3 in figure 28 that the evaporation of the winter RM3 blends is marginally higher and it can be seentoanextentbetweentemperaturesof45oC95oC.
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Temperature(C)
Base RM3
Distillate(in%)

Figure28DistillationcurveofbasegasolineandRM3(winter)
ThepossibleeffectsofRM3blendsondriveabilityandenvironmentalimpactinIcelandare mentionedbelow: Front End: The major change in the distillation curve of the winter RM3 blend from the gasoline is in the front end. According to this, effects of hot driveability, such as poor hot starting, vapour lock and high evaporative losses are expected. However, the general ambient temperatures in Iceland during winter are very low. This means even though the RVP of winter RM3 blend, measured at 37.8oC, is higher the actual evaporative emissions are expected not to increase to the same extent due to very low ambient temperatures. Furthernoissuesofhotstartingareexpectedduetothespecificambientconditions. ThecalculatedresultsforvapourlockindexforsummerRM3iswithinthegeneralstandard referenceofEN228andthusvapourlockisnotexpectedtohappen.Thecalculatedresults forvapourlockindexasfollows(wintergasoline):
Table31VapourlockindexresultsforwinterRM3
Properties Distillation(70 C)(Vol%) RVP(kPa) Vapourlockindex

o
Results(RM3) 30.55 102.13 1235.15
Results(gasoline) 27.9 86.7 1062.3
EN228standard 50.00(max.) 100.0(max.) 1250(max.)
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Midrange and back end: No significant differences in distillation curves of RM3 and gasolineareobserved.ThusnodrivabilityissuesareexpectedforwinterRM3blendforthis range. 8.3 DRIVEABILITYOFTHEVEHICLESWITHRM3ASFUELLITERATURESTUDY
ReviewandanalysisconductedattheRadomTechnicalUniversity,Poland,showedthatthe use of low volume gasoline methanol blends (23 % v/v methanol) has positive effect on the performance with higher octane number, higher efficiency, cleaner combustion and no driveability issues. The review showed that methanol gasoline blends (over 15 % v/v methanol) shall require some minor modifications in the vehicle. However, running on low volume(23%v/vmethanol)donotneedanymodifications.(Kowalewicz,A.(1993))[19]. Fleet testing programme was conducted by Faculty of Mechanical Engineering at Israel Institute of Technology in the year 1985, with 3% methanol blend with gasoline in 1985. Predominantly, the models participated in the fleet were carburettor engines with 14000 vehicles. Fleet testing was conducted for ten months on regular basis in different parts of theIsraelindifferentweatherconditions.ThetemperatureinIsraelvariesfrom0oCto50oC indifferentlocations.(Gutman,Stotter,Borik,&Cernia,1987)[20] Tests were conducted on over more than different 24 different vehicle models for performance,driveabilityandmaterialcompatibility.Fromthetestresultsitwasfoundthat there was no driveability problems associated with the gasoline methanol mixtures even the RVP of the gasoline methanol mixture was above the maximum limits during the summerweatherconditions.(Gutman,Stotter,Borik,&Cernia,1987)[20] Since 1980s fuel system technology has changed from carburettors to the intelligent fuel injection system which controls the airfuel mixture. The positioning of the fuel systems have been carefully placed to avoid any hotdriveability issues due the over evaporation of thefuelinthefuelsystemfromtheexternalheatsources. 8.4 COMPATIBILITYOFRM3WITHFUELSYSTEMS
Increased use of alcohols in gasoline raised concerns on compatibility of the blends with fuel system materials. Especially these were concerns that the oxygen present in the fuel could lead to corrosion. Corrosion is the deterioration of the material due to the chemical
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reaction with the material. Care should be taken to ensure compatibility for blending of methanol,themostcorrosivealcohol,intogasoline. Coppercorrosion Copper strip corrosion test has been conducted by Carbon Recycling International at Fjolver,Reykjaviktoverifycompatibilityofthegasoline/alcoholmixtureswithcopperbased metal parts of fuel systems in vehicles. The test was conducted according to the European standardized test procedure (EN ISO 2160), where the copper strip is heated at 50oC for threehoursinthegasoline/methanolmixtureandthencopperstripisinspectedforcolour. Theresultobtainedfromthetestshowsthegasoline/methanolmixture(RM3)iswithinthe classificationofclassAasspecifiedintheEN228document.Thegasoline/methanolmixture of 3% methanol with gasoline is compatible with the vehicles parts, especially made of copper. Othermaterialcompatibility MethanolingasolinecancausevariousElastomerstoswellandlosetensilestrength,giving rise to possible failure of some critical components. However, gasoline itself being a mixtureofvarioushydrocarbonshascertainmaterialcompatibilityissues.EcotrafficEnergy Research Development Demonstration and Deployment AB, a consulting company in Sweden, developed a report to address concerns regarding material compatibility with methanolandethanol. Standardized tests were conducted (SAE J1681) to determine the material compatibility withmethanol,ethanolandcomparisonwithgasoline. Tests results obtained from the DuPont chemical manufacturers on different materials testedwiththemethanol,ethanolincomparisontogasoline.Fromthetestresultsitcanbe seen that compatibility with the various Elastomers is higher with methanol and ethanol thanthegasoline.(Ahlvik,&Eriksson,2007)[21]
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Table32Elastomersresistancetomethanol,ethanolandgasolineDesignoffleettestingprogram
Thetable32istakenfromthereferencepaperDistributionstrategyforDMEand methanolontheSwedishfuelmarket(Ahlvik,&Eriksson,2007)[21]. TounderstandandconfirmtheeffectsofRM3blendonexistingvehicletechnologyitwould beadvantageoustoperformafleettestingofRM3inIceland.Asapartofcurrentresearch, fleet testing program has been designed on the identified areas that are subjected to be affected. The objective of performing the fleet testing program is to observe the outcome of the vehicles for their performance, driveability and compatibility with RM3 as a fuel. In this fleet test four or more vehicles will be operating on RM3 fuel for at least twelve weeks. Vehicles will be driven on everyday basis and observations will be recorded by the drivers and notified to the representatives of the companies. This fleet testing program is a joint testconductedbythefollowingparticipantcompanies:
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Table33Participantsoffleettestingprogramandduties
Participants No.ofVehicles Duties 1. Brimborg one Inspectionofvehicles 2. CarbonRecyclingInternational one Designofexperiments 3. Olis two Settingupofthegasstation 4. IcelandicInnovationCenter Publishingofdataandreporting 5.Securitas >4 Provisionofvehicles Theidentifiedtestshavebeencategorizedintofivesections. 1. Performancetests 2. Driveabilitytests 3. Compatibilitytests 4. Lubricanttests 5. Emissiontests The above mentioned tests have been identified for the fleet tests and methodology has been developed to perform the tests and identify the cause of any possible problem by suitable methods. In the fleet testing, data will be collected by the drivers and technicians. ThecollecteddatashallbeprocessedbytheIcelandicInnovationcenter(NMI). 8.4.1 Performancetests FuelConsumption I. Objective This test is to determine the fuel consumption of the vehicle on the gasoline methanolblendandtocomparetheresultsfromthevehiclesdrivenonthegasoline fuel. This is a general comparison reporting to compare the results between the fuels. Responsibleforthetests x Driversareresponsibleforperformingthetests. Frequencyoftest x Thisreportingmustbedaily x Thistestshallbeongoingfor12weeksofthefleettest Methodology
II.
III.
IV.
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x x V.
Thedrivermustmakenoteofthequantityofthefueleverytimeafterrefuelling Drivermustalsoreporttheodometerreadingondailybasis.
VI.
Dataacquisition x Thedatashallbetakenfromtheodometerforthedistancecovered x Thedataforthefuelcanbetakenfromthefuelstation Validityofthetest x Thistestisforgeneralcomparisonofthefuelconsumptionbetweenthegasoline and methanol gasoline blend. The results obtained will be based on different driving conditions and patterns. This test is not suitable to determine the fuel consumptionprecisely Qualityassurance x The readings must be taken correctly by the drivers as mentioned in the methodology x Careful methods have to be implemented avoid spillage and reduce the evaporationlossesoffuelduringrefuelling Acceptableoutcome x The difference between the fuel consumption between the gasoline methanol blendsandgasolinemustbewithintheacceptablelimit
VII.
VIII.
BreakMeanEffectivePressure[BMEP] BreakMeanEffectivePressureisthepressureexertedonthepistonheadduringthepower stroke from the top dead centre to the bottom dead centre. This test is to compare the results of the BMEP measured from the vehicles driving on methanol gasoline blend and gasolinefuel. I. Responsibleforthetest x Brimborgisresponsibleforperformingthistest Frequencyofthetest x The measurement for the BMEP can be taken beginning and the end of the fleet test Methodology:
II.
III.
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x The measurement of the BMEP can be measured from the transducers attached
totheengine IV. Dataacquisition x Thedatacanbetakenfrompressuretransducersmountedontheengine Validityofthetest x The results for the BMEP will be measured by the Brimborg technicians. The changeintheBMEPmayhaveeffectontheperformanceoftheengine QualityAssuranceofthetest x TobedecidedbyBrimborg
V.
VI.
8.4.2 Driveabilitytests Vapourlock The vapour lock is caused when the fuel lines of the vehicle is chocked with the vaporized fuel. I. Responsibleforthetests x Drivers are responsible for performing the test. Brimborg is responsible for investigationofanystartingproblemorvapourlockincidents II. Frequencyoftest x Driversmustnoteofanyincidentofstartingproblemandvapourlockincidents Methodology x If the starting of the engine becomes difficult after the routine drive of the vehicle the remarks must be noted by the driver and must be consulted by the techniciansregardingtheprobleminstartingofengine x The drivers and technicians remarks must be notified to the Olis and Carbon RecyclingInternational Dataacquisition x Therearenodirectmethodstodeterminethevapourlockinthevehicles. x Thedrivermusttakethedateandtimeofeveryincidentinstartingoftheengine Validityofthetest
III.
IV.
V.
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The results for the vapour lock will be based on the technicians and drivers remark
VI.
VII.
VIII.
QualityAssurance x Theinvestigationmustbecarefullyconductedbythetechnicians x To determine the cause of the vehicles starting problems indepth investigation oftheproblemisrequiredifthestartingproblempersists Acceptableoutcome x Thereshouldbenovapourlockproblemsinthevehicle Finalreport x Final report shall be prepared by the NMI based on the drivers and technicians comments
Coldstart Whenvehiclesengineiscoldandmethanolgasolineblenddonotproduceairfuelratio withinignitablerangecoldstartproblemsoccur. I. Responsibleforthetests x Brimborgisresponsibleforperformingthetest Frequencyoftest x Technicians are responsible to perform tests on the engine every time it faces startingproblem Methodology x Cold starting occurs when the engine is cold and the air/fuel mixture is not enough to ignite inside the engine. If this problem occurs in the vehicle the drivermustnotetheremarkandconsultthetechnicianregardingtheproblemin thestartingoftheengine. x The drivers and technicians remark must be notified to the Olis and Carbon RecyclingInternational Dataacquisition x Therearenodirectwaystodeterminethecoldstartingproblemsinthevehicles
II.
III.
IV.
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x The driver must take the note of the time and date every time the starting
V.
problemoccurs Validityofthetest x Thetestresultswillbebasedonthecommentsfromthedriversandtechnicians QualityAssurance x The investigation must be carefully conducted by the technicians. To determine thecauseofthevehiclesstartingproblemsindepthinvestigationoftheproblem isrequired Acceptableoutcome x Thereshouldbenocoldstartproblemsrelatedtothevehicle Finalreport x Final report shall be prepared by the NMI based on the drivers and technicians comments
VI.
VII.
VIII.
8.4.3 Compatibilitytests Compatibility tests are performed to determine the compatibility of the vehicles components and parts with the fuel. Any effect on the components of the vehicle will be determined by the visual inspection of the vehicle. The identified compatibility tests are as follows: x x x x x x I. Inspectionoffuelpumps Inspectionofsparkplugs Inspectionoffueltanks InspectionoftheElastomersandplasticsofthefuelsystem Inspectionfortheleaksandcracks Inspectionforthefuelfilters Responsibleforthetests x Brimborgisresponsibleforperformingthetests Frequencyofthetest
II.
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III.
The visual inspection tests for the compatibility have to be performed once in every3weeks Methodology x Pictures of the above mentioned components and parts have to be taken before start of the fleet test. The pictures have to be taken in the presence of the representatives of the Brimborg, Olis, Carbon Recycling International and NMI(Innovationcentre,Iceland) x Notes has be taken of any identified flaw by the representatives of Brimborg, Olis,CarbonRecyclingInternationalandNMI(Innovationcentre,Iceland)
x x
Pictures of the components identified above have to be taken before and after thefleettest.Thepictureshavetotakenbythesamepersonandcameraunder similar light conditions under a controlled environment before and after the tests
IV. DataAcquisition x Datahastobecollecteddirectlyfromthevisualinspectionandthenotesofthe identifieddifferencesmustbetakenaftertheagreementoftherepresentatives oftheBrimborg,OlisandCarbonRecyclingInternational Validityofthetest x The results obtained from the inspection tests are general tests for the comparison purposes. Any differences found should be sent for further tests to determinetheexactcauseoftheproblem Qualityassurance x The tests have to be performed under similar conditions and controlled conditions. The test results obtained will be based on the visual inspection performed on the components and parts of the vehicle. The identified differenceswillbethecollectivediscussionoftherepresentatives Acceptableoutcome x Nodifferenceintheautomobilepartsandcomponentsshouldbevisible
V.
VI.
VII.
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x Asmalldifferenceinthecomponentpartsishoweveracceptable
VIII.
Finalreport x FinalreportmustbepreparedbytheNMI
8.4.4 Enginelubricantoiltests Oil sump test is conducted to find for any worn metal particles from the piston or the engine cylinder due to metalmetal rubbing. This happens when the methanol from the cylinder evaporates and reaches the cylinder head which washes off the lubricant of cylinderwallsanddrainsdowntooilsump.Duetolackoflubricantoncylinderwalls,direct metal to metal contact rubbing causes metal pieces to fall in the oil sump and causing engine cease. Methanol mixes with the lubricant oil in the sump and decreases minimum requiredviscosityofthelubricantoil. I. Responsiblefortests x Brimborgisresponsibleinperformingtheexperiments Frequencyofthetest x Oilsumptestmustbeconductedatthebeginningandendofthefleettest Methodology x Technicians must inspect oil sump for the metal pieces and viscosity of lubricant oilinthesump Dataacquisition x Tobedecidedbythetechnicians Validityofthetests x Tobedecidedbythetechnicians QualityAssurance x Tobedecidedbythetechnicians Acceptableoutcome x Nopresenceofanymetallicpartsintheoilsump x Viscosity of the oil should be within the driving limits as per the vehicles technicalmanual
II.
III.
IV.
V.
VI.
VII.
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VIII.
Finalreport x FinalreportshallbepreparedbytheNMI
8.4.5 Emissiontests Emission tests have to be conducted on the vehicles to identify the change in Carbon monoxide,hydrocarbonandNOxemissions. I. Responsiblefortests x Brimborgisresponsibleinperformingtheemissiontests Frequencyofthetest x Testforemissionsmustbeperformedbeforeandafterthefleettest Methodology x Thetesthastobeconductedforemissionsbyagasanalyser x TheresultsmustbenotifiedtoCarbonRecyclingInternational,OlisandNMI Dataacquisition x Emissionsdatashallbeobtainedfromgasanalyser Validityofthetest x Test results obtained from the emissions test shall be used for the comparison purposes QualityAssurance x The results obtained from the emission tests shall vary with the make and age ofthevehicle AcceptableOutcome x EmissionresultsmustcomplywiththeIcelandicvehicularemissionregulatory Finalreport x NMIshallmakethefinalreportfromtheresultsobtained SUMMARY
II.
III.
IV.
V.
VI.
VII.
VIII.
8.5
Distillation curve of a fuel could affect the driveability of SI engine. Summer and winter RM3 blends distillation curves (section 5) are compared with summer and winter gasoline
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respectively. The midrange and the back end range of summer RM3 distillation curve deviated to an extent compared to summer gasoline. The front end of winter RM3 distillation curve deviated only marginally compared to winter gasoline. No driveability issues are expected based on the distillation curves which is confirmed based on fleet testingtrialsforRM3literature. Copper strip corrosion tests on RM3 blend showed no corrosion effects on copper. Studies indicated that methanol has positive effects on some Elastomers compared to gasoline. Practical fleet test trials should be performed to validate the driveability and compatibility of RM3 on existing vehicle technology. A fleet testing program was designed as a part of theresearchandsubmittedasarecommendationtoCRI.
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9 CONCLUSIONANDRECOMMENDATIONS
In order to use RM3 as a fuel in Iceland, it has to comply with the legislation specifications giveninIcelandsregulatoryofficialdocumentforfuelqualityinnr.560/2007. 9.1 CONCLUSIONS
ThefirstobjectiveoftheresearchwastodeterminethepropertiesoftheRM3blendfor compliancewiththelegislationspecifications. Basegasoline(97%)+RM(3%)RM3tomeetnr.560/2007 Properties which are controlled by the legislation specification were tested for compliance withthelegislationforsummerandwinterRM3andtheobtainedresultsfromthetestsare summarizedasfollows:
Table34AcceptabilityresultsforsummerandwinterRM3
Property ResearchOctaneNumber MotorOctaneNumber Vapourpressure Distillation Percentageevaporatedat100oC Percentageevaporatedat150oC Hydrocarbonanalysis Olefins Aromatics Benzene Oxygencontent Oxygenates Methanol Ethanol Isoprpylalcohol Tertbutylalcohol Isobutylalcohol
Acceptability forsummerRM3 y y n y y y y y y y y y y y
Acceptability forwinterRM3 y y y y y y y y y y y y y y
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Ethers(C5+) Otheroxygenates Sulphurcontent Leadcontent
y y y y
y y y y
It can be seen that all the summer and winter RM3 properties are in compliance with the legislation specification except for Reid vapour pressure for summer RM3. The RVP of the gasoline which was supplied to CRI was at 67.13 kPa and blending of 3% of RM in gasoline increased the RVP of the RM3 to 80.93 kPa, while the legislation specification is 70 kPa. Technical methodology can be employed to optimize the summer RM3 blend by using higher alcohols as cosolvents to reduce the RVP to comply with the legislation specification. The second objective was to look into the above mentioned technical methodology to optimizesummerRM3blendtomeetthelegalrequirementsinIceland. Summerbasegasoline(x%)+cosolvents(y%)+RM(3%)RM3tomeetnr.560/2007 From the below table 35 it can be seen that by using higher alcohols as cosolvents, the summer RM3 blends RVP reduced to some extent but could not meet the required target of70kPa.
Table35RVPresultsforsummerRM3withcosolvents
Fuelblend Summerbasegasoline SummerRM3 SummerRM3+3%Ethanol SummerRM3+3%1Propanol SummerRM3+3%2Propanol SummerRM3+3%1Butanol SummerRM3+3%TBA
RVPin kPa 67.13 80.93 79.56 76.93 77.70 79.10 77.00
From the literature study it was learned that the RVP of summer RM3 can be brought in compliance with the legislative specifications by obtaining low RVP gasoline of approximately 57 kPa. INTROMET program in Sweden successfully developed 3% methanol
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blend in gasoline to meet legislative RVP specifications by using low RVP gasoline with RVP of59kPa. The third objective of the research was to conduct secondary research and tests to determine the effects of RM3 blend on engines for performance, driveability, compatibility andemissions. By utilizing RM3 in engines the engine efficiency is expected to increase. This increase in theengineefficiencyisexpectedtooffsetthecalorificvalueduetomethanolandmaintain the fuel economy as base gasoline. From the conducted engine test it is observed that the torque and power of the engine decreases by ~9% RM3 blend at lower speeds and becomesalikegasolinewiththeincreaseinenginespeed. EmissiontestsperformedshowedthatRM3blendwouldgivebetteremissionperformance thanbasegasoline.COandHCemissionsdecreasedtoagreatextentastheoxygencontent intheRM3blendpossiblyresultedincompletecombustionofthefuelinsidetheengine. Distillation characteristics of summer and winter RM3 blends were compared with their respective base gasoline. Even though minor variations were identified in the distillation curvesduetotheconcernedambientconditionsnodriveabilityeffectsareexpectedforthe RM3blends. The RM3 blends passed the reference copper strip corrosion test and their effect on Elastomers was compared with gasoline. It was observed that for the given set of Elastomers, frequently used in fuel systems, compatibility with methanol was better compared to gasoline. However, by no means this set of Elastomers is a representative of allthematerialsusedintodaysvehiclesfuelsystem. 9.2 RECOMMENDATIONS
DevelopmentandtestofRM3withtargetRVP Fromsection6.4, INTROMETtestresultsshowsthatblendingof3%methanolintolowRVP gasoline could reach the target RVP of RM3 blend. CRI should obtain low Reid Vapour Pressuresummerandwintergasolineandperformblendtestingexperimentswithsummer and winter RM3. Cosolvents could be used if required to reach the target reference specification.
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ImprovementofphasestabilityofRM3byadditionofcosolvents From the obtained results for phase stability in section 5.6, it was observed that the water content in RM3 must not exceed 0.055% w/w at room temperature to ensure phase stability.Itdidnotmeetthereferencespecificationofphasestability0.2%w/wofwaterat room temperature. The table 36 below shows the phase stability of gasoline; methanol gasoline(10wt%)blends;methanolgasolineblendswithcosolvents.
Table36Phaseseparationofmethanolgasolineblendsatspecifiedtemperatureswithwater content
Temperature
Methanol gasoline (10%) ~0%w/w ~0.2%w/w
12oC 15.5 C
o
Methanol gasoline (10%)+5% ethanol ~0.2%w/w
Methanol Methanol gasoline gasoline(10%)+ (10%)+5% 5%1Propanol 2Propanol ~0.25%w/w ~0.4%w/w ~0.65%w/w
~0.45%w/w ~0.55%w/w
The data from shown in the table 36 is taken from the figure 26 (Bechtold, Goodman & Timbario)(2007))[12]. It can be seen that phase separation occurs in methanol gasoline blends at lower water content,byaddingofcosolvents,phasestabilityofthemethanolgasolineblendsimproves evenatverylowtemperatures,asshownintheabovetable.Inordertoimprovethephase stability of the methanol gasoline blends, cosolvents 1propanol and 2propanol as a co solvent may be added to reach the reference specification for phase stability at 0.2 % w/w ofwatercontentatroomtemperature.Duetothewideavailabilityofbioethanolitcanbe usedasacosolvent,italsoreducesthegreenhousegasemissions.
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Figure20Watertoleranceofgasolinewithcosolvents
Thefigure26istakenfromthedocumentUseofMethanolasaTransportationFuel (Bechtold,Goodman&Timbario)(2007))[12]. Controlofwaterinlogistics Methanolhaswaterabsorbingquality,duethisqualityanywaterabsorbedbyRM3abovea certain limit will decrease phase stability and blends may phase separate. Control of water must be checked in logistics to avoid any phase stability problems to occur during transportationandstorage. IndepthtestsforvehiclesperformanceanddriveabilityonRM3blends Indepth engine tests need to be conducted to gather better understanding the effects on engines with summer and winter RM3 blends such as fuel economy, break mean effective pressure. The results obtained from the dynamometer tests in section 7.2 are the results from one test. In order to validate the secondary research discussed in section 7.1, it is requiredtoperformtestsinsteadystateandtransientstateconditionwithdifferentengine
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parameters. Further, driveability tests have to be conducted in different driving, weather and load conditions to determine the effects of summer and winter RM3 blends on driveability. As can be noticed from the obtained distillation characteristics results for summer and winter RM3, there is a slight distortion in the comparison curve of gasoline and RM3. Further tests have to be conducted to determine the effects of distortion in the distillationcharacteristiccurveonthedriveabilityofthevehicle. Assuranceformaterialcompatibility As mention in section 8.4, copper strip corrosion test is conducted to determine the material compatibility with the RM3 blends. Vehicles fuel systems also comprises of differentmaterialssuchasElastomers,plasticsandrubberetc.Methanolbeingacorrosive, it may affect the material properties of the vehicle. Therefore, it is essential to obtain warranty certificates from the vehicle manufacturers for the compatibility of the materials withmethanolgasolineblends.
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REFERENCES
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Anon.,(2008).Commentsregardinglowlevelmethanolfuelblendingstandards forM5M15adoptedbyshanxiprovince(china).Pennsylvania:transportation energyinformationresources 17. Boding,Henrik.(2010).Intrometintroductionofmethanolingasolineusing ethanolascosolvent. Retrievedfromhttp://www.eri.ucr.edu/ISAFXVCD/ISAFXVPP/ItIMG.pdf 18. Bernhardt,W.(1977).Futurefuelsandmixturepreparationmethodsforspark ignitionautomobileengines.Sixteenth(International)SymposiumonCombustion, MassachusettsInstituteofTechnology,Cambridge,3(3), Retrievedfromhttp://www.sciencedirect.com/science/article/pii/0360128577900 016 19. Kowalewicz,A.(1993).Methanolasafuelforsparkignitionengines:areviewand analysis.ProceedingsoftheInstitutionofMechanicalEngineers,PartD:Journalof AutomobileEngineering19891996,207. Retrievedfromhttp://archive.pepublishing.com/content/6418463l84030137/ 20. Gutman,M.,Stotter,A.,Borik,S.,&Cernia,B.(1987).Fleettestingofmethanol gasolineblendsinpublicfillingstations.SocietyofAutomotiveEngineers internationalcongressandexpo,Detroit,MI,USA,23Feb1987, Retrievedfrom http://www.osti.gov/energycitations/product.biblio.jsp?osti_id=6513581 (Gutman,Stotter,Borik,&Cernia,1987) 21. Ahlvik,P.,&Eriksson,L.(2007).Distributionstrategyfordmeandmethanolonthe Swedishfuelmarket.Renewablefuelsforadvancedpowertrains, Retrievedfrom http://www.renewfuel.com/fs_documents.php.(Ahlvik,&Eriksson,2007) 22. LiquidpetroleumproductsVapourpressurePart1.Determinationofair saturatedvapourpressure(ASVP)andcalculateddryvapourpressureequivalent (DVPE);EuropeanStandardEN130161:2007 16.
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23.
24.
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26.
MethodsoftestforpetroleumanditsproductsBS2000123:Petroleum productsDeterminationofdistillationcharacteristicsatatmosphericpressure (ISO3405:2000)(IdenticalwithIP1232001);EuropeanstandardBSENISO 3405:2000BS2000123:2001 PetroleumproductsCorrosivenesstocopperCopperstriptest;European standardENIS02160:1998 PetroleumproductsGumcontentoflightandmiddledistillatefuelsJet evaporationmethod;BSENISO6246:1998 Olah,G.A.,Goeppert,A.,&SuryaPrakash,G.K.(2006).Beyondoilandgas:the methanoleconomy.Weinheim:WileyVCHVerlagGmbH&Co.KGaA,Weinheim.
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APPENDIX
EXPERIMENTALPROCEDURES Experimentalproceduresforperformingthetestsaredevelopedbasedonthestandards andareexplainedbelow. DeterminationofReidVapourPressure(RVP) TheEuropeanstandardsistakenfrom(EuropeanStandardEN130161:2007)[22] 1. Scope:TheEuropeanteststandard(EN130161:2007)specifiesamethodtodetermine the air saturated vapour pressure (ASVP) and dry vapour pressure equivalent (DVPE), which is also the Reid Vapour Pressure (RVP). In this test method vapourtoliquid ratio of 4:1 is taken at 37.8oC. This method describes the determination of the air saturated vapourpressurebetween9.0kPaand150kPaat37.8oC. 2. Principle:Cooledandairsaturatedsampleofmeasuredvolumeisinjectedintothetest chamber evacuated by vacuum pump and under thermostatically controlled temperature at 37.8oC. The temperature of the sample is allowed to reach thermal equilibrium with test temperature of 37.8oC. The resultant pressure will be equivalent to the vapour pressure of sample and air present inside. The dry vapour pressure equivalentcanbecalculatedfromequationDVPE=(0.965ASVP)3.78. 3. Apparatus: I. CoolingequipmentAiroricedwaterbath,capableofcoolingthesamples toatemperaturebetween0oCand1oC. II. Barometerpressuremeasuringdevice,withaccuracyof0.1kPa. III. VacuumgaugeforcalibrationCalibrationdevicecoveringtherangefrom0 kPato0.67kPa. IV. PressuremeasuringdevicePressuremeasuringdevice,rangefrom0kPato 177kPa. V. TemperaturemeasuringdeviceTemperaturemeasuringdevice,withthe resolutionof0.1oCandscaleerrorlessthan0.1oC. VI. SyringeSyringeisusedtotransferthesamplefromthestoragecontainer totheapparatus. VII. Thetestchambermustbevacuumsealedandseptummustbeusedto introducethesampleintothechambereffectively.
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VIII.
4.
Thetestchambermustbeabletomaintainthetemperaturewiththe accuracyof0.1oCandthetemperaturemeasuringinstrumentresolution mustbeatleast0.1oC. IX. Theapparatusshallbecapableofmeasuringthevapourpressurefromthe rangeof9.0kPato150kPawithanaccuracyof0.8kPaandresolutionof0.1 kPa. X. Thevacuumpumpmustbeabletoreduceto0.1kPainthechamber. ProcedureandCalculation:
A 3ml airsaturated liquid sample is injected, using a special gastight syringe through a septum on the top of the unit, into the fully evacuated and sealed 15ml chamber. Pressure readings are then evaluated at one minute intervals: when the pressure reading reaches a value which is stable within 0.1kPa for three minutes the value is recorded as the prescribed end point of the test. The pressure is sensed by a low volumetric displacement transducer and is electronically converted using correlation equationsappropriatetotheMethodofTestanddisplayedonthedigitaldisplay I. II. Airsaturatedvapourpressurecanbetakenfromdisplayoftheequipment. Dryvapourpressureequivalentcanbecalculatedfromtheequation DVPE=(0.965ASVP)3.78
Repeatability,r The difference in results from the two test results obtained by the same operator with same apparatus under constant operating conditions and under the identical testmaterials.Thedifferenceinthetwotestresultsmayexceedoneintwentycases. x Foronelitercontainer o r=0.006(X+A) o X=averageoftheresultsinkilopascals o A=160kPa x For250mlsamplecontainer o r=1.47kPa Reproducibility,R
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The difference between the two single and independent test results, obtained by different operators working in different laboratories on identical test material, the difference between the two values may exceed the value specified one in twenty cases. x Foronelitercontainer o R=0.01014(X+B) o X=averageofthetestresultsinkilopascals o Bis160kPa x For250mlsamplecontainer o R=2.75kPa
5. Results I. AirSaturatedVapourPressure=______kPa II. DrySaturatedVapourPressure=______kPa 6. Importantmeasures I. Alldevicesusedintheexperimentationproceduremustbecalibratedwith approveddevices. II. Thesamplingmustbedoneverycarefullyasperthestandards. III. Thesamplemustbekeptawayfromhotobjects. IV. Thesamplemustbekeptawayfrommixingwithwater. V. Generalsafetymeasuresmustbefollowedwiththeinflammablematerial. Determinationofdistillationcharacteristicsatatmosphericpressure TheEuropeanstandardsistakenfrom(BSENISO3405:2000BS2000123:2001)[23] 1. Scope: The European test standard (ISO 3405: 2000) specifies experimental methodologyandproceduretodeterminethedistillationcharacteristicsoffuel. 2. Principle: In this experiment, sample fuel is being taken in the apparatus; fuel is distilled under different temperatures under certain specified conditions. Different volumes of the distillate will be recovered at different temperatures. The distillate will be recovered in the graduated cylinder. In nr. 560/2007 legislation of Iceland document two different temperatures have been stated, at 100oC and 150oC. The volume of the distillate will be collected at each different temperature and results willbecomparedtovaluesinthelegislation.
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3. Calculation: I. Todeterminespecifiedpercentevaporatedorrecoveredforasample.Slopeforthe distillation curve can be determined, readings of thermometer must be recorded at every1%(v/v)recovered.Theslopecanbecalculatedfromthefollowingformula: T1,T2,T3=Temperaturesrecordedinthethermometer V1,V2,V3=Volumeofthefuelcollectedateachspecifiedtemperature II. Whenresidualliquidinthedistillationflaskisapproximately5ml,finaladjustments to the heat should be made. Subtract the estimated loss from the 93.5 ml to estimate the amount recovered in the receiver at that time. The time from the 5ml of liquid residue in the distillation flask to the final boiling point shall be within the limits specified. If the final boiling point is not within the specified limits the experiment must be repeated. If the actual residue exceeds the value of 2 ml, repeatthetest. III. Corrected thermometer readings must be obtained. Tc to be applied to each thermometerreadingbymeansSydneyYoungequation. Tc=0.0009(101.3pk)(273+t) Pk= barometric pressure prevailing at the time and location of the test, in kilopascals; T=observedthermometerreading,indegreeCelsius IV. Correct the actual loss to 101.3 kPa pressure when thermometer readings are correctedto101.3kPapressure.Calculatethecorrectedloss,Lc,inpercentvolume, fromfollowingequation. Equation(2) V. L=percentlosscalculatedfromthetestdata,inpercentvolume; P=istheobservedbarometricpressure. Calculatethecorrespondingcorrectedpercentrecovery,Rc,inpercentvolume. Rc=R+(LLc) R=observedrecovery,inpercentvolume; L=observedpercentloss,inpercentvolume; Lc=iscorrectedpercentloss,inpercentvolume.
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VI.
VII.
To calculate the percentages evaporated at specified thermometer readings, add the percent loss to each of the percentages recovered at specified thermometer readings. Equation(3) Where, Pe=Percentagevolumeevaporated; Pr=Percentagevolumerecovered; L=Observedpercentloss,percentvolume. Deducttheobserveddistillationlossfromeachspecifiedpercentagesevaporatedin order to obtain the corresponding percentages recovered. Calculate required thermometerreading,T,indegreeCelsius. Equation(4) R = It is the percent volume recovered corresponding to the specified volume evaporated Rh=thepercentvolumerecoveredadjacenttoandhigherthanR; Rl=thepercentvolumerecoveredadjacentto,andlowerthanR; Th=thethermometerreadingrecordedatRh,indegreeCelsius; Tl=thethermometerreadingrecordedatRl,indegreeCelsius.

Precision:TodeterminetheprecisionoftheresultsotherthaninitialBoilingPoint(IBP)and Final Boiling Point (FBP), it is generally necessary to change the rate of change of the temperature at that particular point. This variable C/V, equal to the change in temperaturepercentrecoveredorevaporated. Equation(5)

Tu=uppertemperature. Tl=lowertemperature. Vu=percentvolumerecoveredorevaporatedcorrespondingtoTu. Vl=percentvolumerecoveredorevaporatedcorrespondingtoTl. Testforphasestabilityinthegasolinemethanolblends TheEuropeanstandardsdonotspecifyanystandardexperimentalproceduretodetermine phase stability. But determination of phase stability is an important aspect for test of gasolinemethanolblends.
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Thetestmethodistakenfromthereferencedocument[16] Watercontent 1. Scope:ThescopeofthismeasurementistodeterminethewatercontentintheRM blends,tounderstandtheconditionsofthephasestability. Determinationofphasestabilityatroomtemperature 1. Scope: Test for the phase stability at room temperature by addition of water in RM blends. 2. Procedure:Aknownamountofwaterisaddedintothesampleandwatercontentis measuredwithKarlFischertitrationexperimentandsampleisvisuallyinspectedfor phaseseparationatroomtemperature. Determinationofphasestabilityat30oC 1. Scope:Todeterminethephasestabilityofthegasolinemethanolblendsat30oC. It can also be used to determine the temperature for occurrence of phase separation atgivenspecifiedwatercontentoftheRMblends. 2. Principle: The sample is taken in test tubes to 40 ml and then is placed into the cooling facility. The temperature inside the cooling facility is controlled with a mixture of acetone and dry ice. The sample is inspected for phase separation when temperatureofsamplereaches30oC. 3. Procedure 1. Acetone is poured into cooling facility until the sample containers are at least partiallyimmersedinsideacetoneanddryicemixture. 2. A thermometer is used to determine the temperature of the acetone and dryice mixture. 3. Sample temperature is measured from the placed thermometers in the sample testtubes. 4. Visualinspectionhastobeconductedtoidentifyanyphaseseparation. 5. Phaseseparationtemperaturescanbetakenfromthermometers. DeterminationofthecorrosivenesstothecopperCopperstripcorrosion TheEuropeanstandardsistakenfrom(EuropeanStandard(ENIS02160:1998)[24] 1. Scope: This experiment is conducted to determine corrosiveness to copper strip corrosion. Corrosion can cause damage to the vehicles equipment and also OptimizationoflowvolumeRenewableMethanolblending
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2.
dissolvedcoppercangetoxidizedandcausefurtherdepositformation.Thedeposits canblockthefiltersandthefuelinjectionequipmentofvehicle. Note:ThisexperimentationisperformedexternallyatFjolverslaboratory Principle: In this experiment a polished copper strip is taken and immersed into specified volume of gasoline and heated under specified temperature for the specifiedamountoftimeandstripisremovedatendoftestandvisualinspectionis conductedonthecolourofthecopperstriptodetermineclassofcopperstrip. EN228specification AspertheEN228specificationsthespecifiedcolourmustmatchwithinclass1. AspertheEuropeanstandardsENISO2160:1998,thecolourofclass1arespecified asfollows: Class1 a.) Lightorange,almostsameasafreshlypolishedstrip b.) Darkorange 3. Result: Report classification of the class of corrosion from the classifications given byEuropeanstandards. Corrosioncopperstrip(____h/____0C),Class_____.
Determinationofthegumcontentoflightandmiddledistillatefuels TheEuropeanstandardsistakenfrom(EuropeanStandardBSENISO6246:1998)[25] Evaporationmethod. 1. Scope: This experiment is conducted to determine existent gum content of fuels. Due to the storage of automotive fuel, oxidation occurs and gum is formed. It will separateoutandformsludge.Thegumcontentcanformdepositsinsideengineand cancauseproblems.Itisimportanttodeterminegumcontentofthefuel. Note:ThisexperimentationisperformedexternallyatFjolverslaboratory. 2. Principle: Specified amount of the fuel is taken and fuel is allowed to evaporate under controlled conditions, the fuel is evaporated either by air or steam. The residueiswashedwiththeheptaneandweighedtodeterminegumcontentoffuel. OptimizationoflowvolumeRenewableMethanolblending
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Measurement: 1. A=2000[(m1m3)(m2m4)] Where, A=Itisthegumcontent,expressedasmilligramsper100ml; m1=Itisthemass,ingrams,ofthesamplebeakerplusresidue; m2=Itisthemassingrams,ofthetarebeakeraftertreatment; m3=Itisthemassingrams,oftheemptysamplebeaker; m4=itisthemass,ingrams,ofthetarebeakerbeforetreatment; Result 1. Fornonaviationfuels=_____mg/100ml. StatisticalAnalysis 1. Repeatability,r r=0.882+0.2746x x=averageoftheresultsbeingcompared 2. Reproducibility,R R=1.06+0.5567x x=averageoftheresultsbeingcompared EN228specifications As per the EN 228 specifications, limit for maximum gum content (solvent washed) in the fuel is 5mg /100 ml. The test method to determine gum content of fuel is specified in EN ISO6246. SAFETYREQUIREMENTS All the experiment procedures also include certain safety requirements as directed by operatorsmanual.Someofthemainsafetyrequirementsare: 1. Donottouchthefuelsampleswithoutwearingsafetygloves 2. Alwayswearsafetyglassesandlabcoatwhileperformingtheexperiments 3. Donotinhaleorconsumethesamples
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Reykjavk Energy Graduate School of Sustainable Systems (REYST) combines the expertise of its partners: Reykjavk Energy, Reykjavk University and the University of Iceland. Objectives of REYST: Promote education and research in sustainable energy earth sciences REYST is an international graduate programme open for students holding BSc degrees in engineering, earth sciences or business. REYST offers graduate level education with emphasis on practicality, innovation and interdisciplinary thinking. REYST reports contain the masters theses of REYST graduates who earn their degrees from the University of Iceland and Reykjavk University.

Methanol and Gasoline Blending - Automotive

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Optimization of low volume Renewable Methanol blending

Chivukula Venkata Kalyan

REYKJAVK ENERGY GRADUATE SCHOOL OF SUSTAINABLE ENERGY

REYST report 09-2011

Optimization of low volume Renewable Methanol blending

Thesis Master of Science June 2011

Optimization of low volume Renewable Methanol blending

Ritger til meistaraprfs (MSc)

Optimization of low volume Renewable Methanol blending

Optimization of low volume Renewable Methanol blending

Student: ___________________________________________ C V Kalyan

Examiner: ___________________________________________ Dr. Halldor Palsson

Table1R/Pratio'sofmainfossilfuels Fuel Oil

Reserves 181.7 826001.0 6621.2

R/Pratio(Years) 45.7 119.0 62.8

(1) (2) (3)

Thefigure4isfromresearchpaperProperties,Performance,andemissionsofmethanol gasolineblendsinasparkignitionengine(Qi,Liu,Zhang,Bian,(2004)[11] 2.3 HISTORYOFMETHANOLASFUEL

ChangeinProperties Direct calculation

95 85 46 75

3 RM BLENDING EFFECTS ON GASOLINE PROPERTIES SECONDARYRESEARCH

Referencespecifications Innr.560/2007standardspercentagevolumeofevaporation(In.Nr.560/2007)[13] x E100At1000Cminimumvolumeofevaporationshouldbe46%orabovebyvolume x E150At1500Cminimumvolumeofevaporationshouldbe75%orabovebyvolume ChangeinpropertyduetoRMblending

Standardno. EN130161 ENISO3405 ENISO7536

Thedataintable6istakenfromprintdocumentAutomotivefuelsUnleadedpetrol Requirementandtestmethods(Anon.,(2008))[14]. 4.1 ESTABLISHMENTOFBLENDTESTFACILITY

S.No 1 2 3 Average StandardDeviation

Sample Basegasoline Basegasoline Basegasoline

RVP inkPa 67.00 67.10 67.30 67.13 0.15

S.No 1 2 3 Average StandardDeviation

Sample RM3 RM3 RM3

RVPinkPa 80.70 81.40 80.70 80.93 0.40

S.No 1 2 3 Average StandardDeviation

Sample Basegasoline Basegasoline Basegasoline

RVPinkPa 86.60 86.60 86.50 86.57 0.06

S.No 1 2 3 Average StandardDeviation

Sample RM3 RM3 RM3

RVPinkPa 101.80 102.10 102.40 102.10 0.30

Description Sampleno.1 Sampleno.2 Averageof1and2 Referencespecification

E150(in%) 87 88 87.50 75(min.)

FBP(in0C) 185 184 184.50 210(max.)

Description Sampleno.1 Sampleno.2 Averageof1and2 Referencespecification

E100(in%) 56.95 55.95 56.45 46(min.)

E150(in%) 89.55 89.95 89.75 75(min.)

FBP(in0C) 186 183 184.50 210(max.)

5.2.3 DistillationcurveofbasegasolineVsRM3 TheoveralldistillationcurveofbasegasolineiscomparedwiththatofRM3scurveinfigure 15.

Description Sampleno.1 Sampleno.2 Averageof1and2 Referencespecification

E100(in%) 51.88 51.90 51.89 46(min.)

E150(in%) 84.88 83.90 84.39 75(min.)

FBP(in0C) 186 195 190.50 210(max.)

5.2.5 ResultsfordistillationcharacteristicsofRM3(winter) ThemaindistillationcharacteristicsforwinterRM3werecalculatedandcrosscheckedwith thereferencespecificationsasshownintable16:

Description Sampleno.1 Sampleno.2 Averageof1and2 Referencespecification

E100(in%) 53.03 53.06 53.05 46(min.)

E150(in%) 85.03 85.06 85.05 75(min.)

FBP(in0C) 192.5 193 192.75 210(max.)

5.3.1 Resultforexistentgumcontent Theobtainedresultforexistentgumcontenttestfollows:

5.3.2 Resultforresidue Theobtainedresultforexistentgumcontenttestfollows:

Sample RM3 RM3 RM3 RM3 RM3 RM3

Sample RM3 RM3 RM3

Watercontent%(w/w) 0.0207 0.0267 0.0267

Result Nophaseseparation Nophaseseparation Nophaseseparation

Sample RM3 RM3 RM3

Watercontent% (w/w) 0.0378 0.0346 0.0519 0.0543 0.0779 0.0723

Temperature(0C) roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature roomtemperature

Result Nophaseseparation Nophaseseparation Nophaseseparation Nophaseseparation phaseseparation phaseseparation

Sample RM3 RM3 RM3