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US 8,212,088B2 34 dieselengine.Ifdesired,additivesorignitionimprovers,such asoctylnitrate,tetrahydrofurfurylnitrate,peroxidesorhigher alkylethers,canbeaddedtobringmethanol’scetaneratingto the level closer to diesel. Methanol can also be used in the manufactureofbiodieselfuelsbyesteri?cationoffattyacids. Closely related and derived from methanol, and also a desirable alternative fuel is dimethyl ether. Dimethyl ether (DME, CH3OCH3), thesimplestofalethers,isacolorless, nontoxic,non-corrosive,non-carcinogenicandenvironmen tallyfriendlychemicalthatismainlyusedtodayasanaerosol propellantinspraycans,inplaceofthebannedCFC gases. DME hasaboilingpointof—250C.,andisagasunder ambientconditions.DME is,hoWever,easilyhandledasliq uidandstoredinpressurizedtanks,muchlikelique?edpetro leum gas (LPG). The interest in dimethyl ether as alternative fuelliesinitshighcetaneratingof55 to60,Which ismuch higherthanthatofmethanolandisalsohigherthanthecetane rating of 40 to 55 of conventional diesel fuels. The cetane ratingindicatesthatDME canbeeffectivelyusedindiesel engines.Advantageously,DME,likemethanol,iscleanbum ing, and produces no soot particulates, black smoke or S02, and only very loW amounts of NO,C and other emissions even Withoutafter-treatmentofitsexhaustgas.Some ofthephysi calandchemicalpropertiesDME, incomparisontodiesel fuel, are shoWn in Table 1. TABLE 1 ComparisonofthephysicalpropertiesofDME anddieselfuel 20 25 30 35 structure. Further, methanol has a relatively high theoretical volumetricenergydensitycomparedtoothersystemssuchas conventionalbatteriesandtheHZ-PEM fuelcell.Thisisof great importance for small portable applications (cellular phones, laptop computers, etc.), for Which small siZe and Weightofenergyunitisdesired. TheDMFCoffersnumerousbene?tsinvariousareas, includingthetransportationsector.By eliminatingtheneed for a methanol steam reformer, the DMFC signi?cantly reduces the cost, complexity and Weight of the vehicle, and improvesfueleconomy.A DMFC systemisalsocomparable in its simplicity to a direct hydrogen fuel cell, Without the cumbersome problems of on-board hydrogen storage or hydrogenproducingreformers.BecauseonlyWaterandCO2 are emitted, emissions of other pollutants (e.g., NOX, PM, S02, etc.) are eliminated. Direct methanol fuel cell vehicles are expected to be virtually Zero emission vehicles (ZEV), and use of methanol fuel cell vehicles offers to nearly elimi nate air pollutants from vehicles in the long term. Further, unlikeICEvehicles,theemissionpro?leisexpectedto remainnearlyunchangedovertime.NeW membranes based onhydrocarbonorhydro?uorocarbonmaterialsWithreduced cost and crossover characteristics have been developed that alloW room temperature ef?ciency of 34%. Methanol as indicated provides a number of important advantages as transportation fuel. Contrary to hydrogen, methanol does not require any energy intensive procedures for pressurization or liquefaction. Because it is a liquid at roomtemperature,itcanbeeasilyhandled,stored,distributed andcarriedinvehicles.Itcanactasanidealhydrogencarrier for fuel cell vehicles through on-board methanol reformers, andcanbeuseddirectlyinDMFC vehicles. Methanol is also an attractive source of fuel for static applications. For example, methanol can be used directly as fuel in gas turbines to generate electric poWer. Gas turbines typicallyusenaturalgasorlightpetroleumdistillatefractions as fuel. Compared to such fuels, methanol can achieve higher poWer output and loWer NO,C emissions because of its loWer ?ametemperature.Sincemethanoldoesnotcontainsulfur, SO2emissionsarealsoeliminated.Operationonmethanol offers the same ?exibility as natural gas and distillate fuels, and can be performed With existing turbines, originally designed for natural gas or other fossil fuels, after relatively easy modi?cation. Methanol is also an attractive fuel since fuel-grademethanol,WithloWerproductioncostthanhigher purity chemical-grade methanol, can be used in turbines. BecausethesiZeandWeightofafuelcellisoflessimportance in static applications than mobile applications, various fuel cellsotherthanPEM fuelcellsandDMFC, suchasphospho ricacid,moltencarbonateandsolidoxidefuelcells(PAFC, MCFC, andSOFC,respectively),canalsobeused. Methanol and dimethyl ether are also very convenient materialsforstorageandtransportationofenergyWithoutthe greatdisadvantageandpotentialdangerofusinghydrogen. HydrogencanreadilyconvertedWithCO2tomethanoland/or DME thusprovidingaconvenientsafeformforstoringand transporting energy produced from any source. In addition to these uses as fuels, methanol and methanol derived chemicals have other signi?cant applications in the chemicalindustry.Today,methanolisoneofthemostimpor tantfeedstockinthechemicalindustry.Mostofthe32million tons of annually produced methanol is used to manufacture a largevarietyofchemicalproductsandmaterials,including basic chemicals such as formaldehyde, acetic acid, MTBE (althoughitisincreasinglyphasedoutforenvironmental reasons),asWellasvariouspolymers,paints,adhesives,con structionmaterials,andothers.WorldWide,almost70% of Boilingpoint0C. Vapor pressure at 200 C. (bar) Liquid density at 200 C. (kg/m3) Heatingvalue(kcal/kg) Cetane number Autoignitiontemperature(0C.) Flammabilitylimitsinair(vol%) DME Dieselfuel —24.9 180-360 Currently,DMEisexclusivelyproducedbydehydrationof methanol.AmethodforsynthesiZingDMEdirectlyfrom40 synthesisgasbycombiningthemethanolsynthesisanddehy dration steps in a single process has also been developed. Another methanol derivative is dimethyl carbonate (DMC), Which can be obtained by converting methanol With phosgeneorbyoxidativecarbonylationofthemethanol.45 DMC hasahighcetanerating,andcanbeblendedintodiesel fuelinaconcentrationupto10%,reducingfuelviscosityand improvingemissions. Methanolanditsderivatives,e.g.,DME, DMC, andbiodie sel,havemanyexistingandpotentialuses.Theycanbeused, for example, as a substitute for gasoline and diesel fuel in ICE-poweredcarsWithonlyminormodi?cationstotheexist ing engines and fuel systems. Methanol can also be used in fuelcells,forfuelcellvehicles(FCVs),Whichareconsidered tobethebestalternativetoICEsinthetransportation?eld. DME isalsoapotentialsubstituteforLNG andLPG for heating homes and in industrial uses. 50 55 U.S. Pat. No. 5,599,638 discloses a simple direct methanol fuelcell(DMFC) andaddressesthedisadvantagesofhydro genfuelcells.Incontrasttoahydrogenfuelcell,theDMFC 60 isnotdependentongenerationofhydrogenbyprocessessuch aselectrolysisofWaterorreformationofnaturalgasorhydro carbon. The DMFC is also more cost effective because methanol,asaliquidfuel,doesnotrequirecoolingatambient temperaturesorcostlyhighpressureinfrastructureandcanbe usedWithexistingstorageanddispensingunits,unlikehydro genfuel,WhosestorageanddistributionrequiresneWinfra 5.1 668 6,880 55-60 235 3.4-17 i 840-890 10,150 40-55 200-300 0.6-6.5 65PDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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