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US 8,440,729B2 34 nolburnsaboutfourtimesslowerthangasoline,releasesheat only at one-eighth the rate of gasoline ?re, and is far less likelytospreadtosurroundingignitablematerialsbecauseof theloWradiantheatoutput.IthasbeenestimatedbytheEPA thatsWitchingfromgasolinetomethanolWouldreduceinci dence of fuel-related ?re by 90%. Methanol burns With a colorless ?ame, but additives can solve this problem. As methanol is completely miscible With Water not only it is environmentallyreadilydecomposedinnaturebutincontrast to ethanol there are no strict requirements needed to keep it drytoavoidphaseseparationfromgasoline. Methanol also provides an attractive and more environ mentally-friendly alternative to diesel fuel. It does not pro ducesmoke,soot,orparticulatesWhencombusted,incontrast to diesel fuel, Which generally produces polluting particles duringcombustion.ItalsoproduceveryloWemissionsofNO because itburns at a loWer temperature than diesel. Further more,ithasasigni?cantlyhighervaporpressurecomparedto diesel fuel, and the higher volatility alloWs easy start even in coldWeather,Withoutproducingsmoketypicalofcoldstart20 With a conventional diesel engine. Ifdesired, additives or ignition improvers, such as octyl nitrate, tetrahydrofurfuryl nitrate,peroxidesorhigheralkylethers,canbeaddedtobring methanol’s cetane rating to the level closer to diesel. Metha nolisalsousedinthemanufactureofbiodieselfuelsby25 esteri?cationoffattyacids. hasahighcetanerating,andcanbeblendedintodieselfuelin a concentration up to 10%, reducing fuel viscosity and improvingemissions. Methanol and its derivatives, e.g., dimethyl ether, DMC, andbiodieselfuel(estersofnaturallyoccurringunsaturated acids)alreadyhavesigni?cantandexpandinguses.Theycan be used, for example, as a substitute for gasoline and diesel fuel in lCE-poWered cars With only minor modi?cations to the existing engines and fuel systems. Methanol can also be used in fuel cells, for fuel cell vehicles (FCVs), Which are considered to be the best alternatives to lCEs in the transpor tation?eld.DME isalsostartingtobeusedinadmixtureto LNG andLPG indomesticandindustrialfueluses. Methanol can also be used in reforming to produce hydro gen. In an effort to address the problems associated With hydrogen storage and distribution, suggestions have been made to use liquids rich in hydrogen such as gasoline or methanol as a source of hydrogen in vehicles via an on-board reformer. ItWas emphasiZed thatmethanol isthe safestofall materialsavailableforsuchhydrogenproduction.Further, because of the high hydrogen content of liquid methanol, evencomparedtopurecryogenichydrogen(98.8gofhydro gen in a liter of methanol at room temperature compared to 70.8 g in liquid hydrogen at about —253° C.), methanol is an excellentcarrierofhydrogenfuel.TheabsenceofC4C bonds in methanol, Which are more dif?cult to break, facili tatesitstransformationtopurehydrogenin80to90% e?i ciency. In contrast to a pure hydrogen-based storage system, a reformersystemiscompact,containingonavolumebasis morehydrogenthanevenliquidhydrogen,andiseasytostore and handle Without pressurization. A methanol steam reformerisalsoadvantageousinalloWingoperationatamuch loWer temperature (2500 C. to 350° C.) and for being better adaptedtoon-boardapplications.Furthermore,methanol contains no sulfur, a contaminant for fuel cells, and no nitro gen oxides are formed from a methanol reformer because of theloWeroperatingtemperature.ParticulatematterandNO,C emissions are virtually eliminated, and other emissions are minimal.Moreover,methanolalloWsrefuelingtobeasquick and easy as With gasoline or diesel fuel. Thus, an on-board methanol reformer enables rapid and ef?cient delivery of hydrogen from liquid fuel that can be easily distributed and As mentioned, the closely related derivative of methanol, Whichisahighlydesirablealternativefuel,isdimethylether. Dimethylether(CH3OCH3), thesimplestofalethers,isa colorless,nontoxic,non-corrosive,non-carcinogenicand30 environmentallyfriendlychemicalthatismainlyusedtoday asanaerosolpropellantinspraycans,inplaceofthebanned CFC gases.Dimethyletherhasaboilingpointof—25°C.,and isagasunderambientconditions.Dimethyletheris,hoWever, easilyhandledasaliquidandstoredinpressurizedtanks,35 much like lique?ed petroleum gas (LPG). The interest in dimethyletherasalternativefuelliesinitshighcetanerating of55to60,Whichismuch higherthanthatofmethanolandis also higher than the cetane rating of 40 to 55 of conventional dieselfuels.Thecetaneratingindicatesthatdimethyletheris40 effectivelyusedindieselengines.Advantageously,dimethyl ether, like methanol, is clean burning, and produces no soot particulates, black smoke or S02, and only very loW amounts ofNO,CandotheremissionsevenWithoutafter-treatmentofits storedinthevehicle.Todate,methanolistheonlyliquidfuel exhaustgas.Someofthephysicalandchemicalpropertiesof45 DME, incomparisontodieselfuel,areshoWninTable1. thathasbeendemonstratedonapracticalscaletobeasuitable liquidfuelforareformertoproducehydrogenforuseinafuel cellsfortransportationapplications. In addition to on-board reforming, methanol also enables convenient production of hydrogen in fueling stations for refuelinghydrogenfuelcellvehicles.A fuelcell,anelectro chemical device that converts free chemical energy of fuel directlyintoelectricalenergy,providesahighlyef?cientWay ofproducingelectricityviacatalyticelectrochemicaloxida tion.Forexample,hydrogenandoxygen(air)arecombinedin anelectrochemicalcell-likedevicetoproduceWaterandelec tricity. The process is clean, With Water being the only byproduct. HoWever, because hydrogen itselfmust ?rst be produced in an energy-consuming process, by electrolysis or from a hydrocarbon source (fossil fuel) With a reformer, hydrogenfuelcellsarestilnecessarilylimitedintheirutility. A systemforproducinghighpurityhydrogenhasbeen developed by steam reforming of methanol With a highly active catalyst, Which alloWs operation at a relatively loW temperature (2400 C. to 2900 C.) and enables ?exibility in operationasWellasrapidstart-upandstop.Thesemethanol to-hydrogen (MTH) units, ranging in production capacity from50to4000m3 H2perhour,arealreadyusedinvarious TABLE 1 ComparisonofthephysicalpropertiesofDME anddieselfuel 50 55 60 Another methanol derivative is dimethyl carbonate 65 (DMC), Which can be obtained by converting methanol With phosgene orby oxidativecarbonylationofmethanol. DMC Boiling point ° C. Vapor pressure at 20° C. (bar) Liquid density at 20° C. (kg/m) Heatingvalue(kcal/kg) Cetane number Autoignitiontemperature(°C.) Flammabilitylimitsinair(vol%) Dimethyl Ether Diesel Fuel —24.9 180-360 5.1 4 668 840-890 6,880 10,150 55-60 40-55 235 200-300 3-17 0.6-6.5 Currently,dimethyletherisproducedbythedirectdehy dration of methanol according to the folloWing reaction:PDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL BIOREFORMING
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