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US 7,906,559B2 34 rialsbecauseoftheloWradiantheatoutput.Ithasbeenesti mated by the EPA that switching from gasoline to methanol Wouldreduceincidenceoffuel-related?reby 90%. Methanol burns With a colorless ?ame, but additives can solve this problem. As methanol is completely miscible With Water not onlyitisenvironmentallyreadilydecomposedinnaturebutin contrasttoethanolthereareno strictrequirementsneededto keepitdrytoavoidphaseseparationfromgasoline. Methanoland/orDME alsoprovideanattractiveandmore environmentally-friendly alternative to diesel fuel. They do notproduce smoke, soot,orparticulatesWhen combusted, in contrast to diesel fuel, Which generally produces polluting particles during combustion. They also produce very loW emissionsofNOx becausetheyburnataloWertemperature than diesel. Furthermore, they have a signi?cantly higher vaporpressurecomparedtodieselfuel,andthehighervola tility alloWs easy start even in cold Weather, Without produc ing smoke typical of cold start With a conventional diesel engine.Ifdesired,additivesorignitionimprovers,suchas 20 octylnitrate,tetrahydrofurfurylnitrate,peroxidesorhigher alkylethers,canbeaddedtobringmethanol’scetaneratingto the level closer to diesel. Methanol is also used in the manu facture of biodiesel fuels by esteri?cation of fatty acids. Asmentionedcloselyrelatedandderivedfrommethanol, 25 andhighlydesirablealternativefuelisdimethylether.Dim ethylether(DME, CH3OCH3), thesimplestofalethers,isa colorless, nontoxic, non-corrosive, non-carcinogenic and environmentallyfriendlychemicalthatismainlyusedtoday asanaerosolpropellantinspraycans,inplaceofthebanned 30 CFCgases.DME hasaboilingpointof—250C.,andisagas underambientconditions.DME is,hoWever,easilyhandled asliquidandstoredinpressurizedtanks,much likelique?ed petroleum gas (LPG). The interest in dimethyl ether as alter nativefuelliesinitshighcetaneratingof55to60,Whichis35 muchhigherthanthatofmethanolandisalsohigherthanthe cetane rating of 40 to 55 of conventional diesel fuels. The cetaneratingindicatesthatDME canbeeffectivelyusedin dieselengines.Advantageously,DME, likemethanol,isclean burning,andproducesnosootparticulates,blacksmokeor 40 S02, and only very loW amounts ofNO,C and other emissions evenWithoutafter-treatmentofitsexhaustgas.Some ofthe physical and chemical properties DME, in comparison to diesel fuel, are shoWn in Table 1. Methanolanditsderivatives,e.g.,DME, DMC, andbiodie sel(estersofnaturallyoccurringunsaturatedacids)already have signi?cant and expanding uses. They can be used, for example, as a substitute for gasoline and diesel fuel in ICE poWered cars With only minor modi?cations to the existing engines and fuel systems. Methanol can also be used in fuel cells,forfuelcellvehicles(FCVs),Whichareconsideredtobe thebestalternativestoICEs inthetransportation?eld.DME isalsostartingtobeusedinadmixturetoLNG andLPG in domestic and industrial fuel uses. 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 materials available for such hydrogen production. Further, because of the high hydrogen content of liquid methanol, evencomparedtopurecryogenichydrogen(98.8gofhydro geninaliterofmethanolatroomtemperaturecomparedto 70.8 g in liquid hydrogen at —2530 C.), methanol is an excel lentcarrierofhydrogenfuel.TheabsenceofC4C bondsin methanol, Which are more dif?cult to break, facilitates its transformationtopurehydrogenin80to90% e?iciency. In contrast to a pure hydrogen-based storage system, a reformer system is compact, containing on a volume basis morehydrogenthanevenliquidhydrogen,andiseasytostore and handle Without pressurization. A methanol steam reformerisalsoadvantageousinalloWingoperationatamuch loWertemperature(250-3500C.)andforbeingbetteradapted to on-board applications. Furthermore, methanol contains no sulfur,acontaminantforfuelcells,andnonitrogenoxidesare formed from a mcthanol rcformcr because of the low operat ing temperature. Particulate matter and NO,C emissions are virtuallyeliminated,andotheremissionsareminimal.More over, methanol alloWs refueling to be as quick and easy as With gasoline or diesel fuel. Thus, an on-board methanol reformer enables rapid and e?icient delivery of hydrogen fromliquidfuelthatcanbeeasilydistributedandstoredinthe vehicle.Todate,methanolistheonlyliquidfuelthathasbeen demonstrated on a practical scale as suitable liquid fuel for a reformer to produce hydrogen for use in a fuel cells for transportationaplications. In addition to on-board reforming, methanol also enables convenientproductionofhydrogeninfuelingstationsfor 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 fromahydrocarbonsource(fossilfuel)Withareformer, hydrogenfuelcellsarestilnecessarilylimitedintheirutility. A systemforproducinghighpurityhydrogenhasbeen developed by steam reforming of methanol With a highly active catalyst, Which alloWs operation at a relatively loW temperature(240-2900C.)andenables?exibilityinopera tion as Well as rapid start-up and stop. These methanol-to hydrogen(MTH)units,ranginginproductioncapacityfrom 50to4000m3 H2perhour,arealreadyusedinvariousindus tries,includingtheelectronic,glass,ceramic,andfoodpro cessingindustries,andprovideexcellentreliability,pro longed life span, and minimal maintenance. As described above, operatingatarelativelyloW temperature,theMTH 45 50 55 60 Another methanol derivative is dimethyl carbonate (DMC), Which can be obtained by converting methanol With phosgene or by oxidative carbonylation of the methanol. DMChasahighcetanerating,andcanbeblendedintodiesel65 fuelinaconcentrationupto10%,reducingfuelviscosityand improvingemissions. TABLE 1 ComparisonofthephysicalpropertiesofDME anddieselfuel Boiling point0 C. Vapor pressure at 200 C. (bar) Liquid density at 200 C. (kg/m3) Heatingvalue(kcal/kg) Cetane number Autoignitiontemperature(0C.) Flammabilitylimitsinair(vol%) —24.9 5.1 668 6,880 55-60 235 3.4-17 180-360 i 840-890 10,150 40-55 200-300 0.6-6.5 Currently,DME isproducedbydirectdehydrationof methanol.PDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL
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