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US 8,440,729B2 56 industries,includingtheelectronic,glass,ceramic,andfood processingindustries,andprovideexcellentreliability,pro longed life span, and minimal maintenance. As described above, operating atarelativelyloW temperature, theMTH process has a clear advantage over reforming of natural gas and other hydrocarbons Which must be conducted at above 600° C., because less energy isneeded to heat methanol to the appropriatereactiontemperature. The usefulness of methanol has led to the development of other reforming processes, for example, a process knoWn as oxidative steam reforming, Which combines steam reform ing,partialoxidationofmethanol,usingnovelcatalystsys tems.Oxidativesteamreformingproduceshighpurityhydro gen With Zero or trace amounts of CO, at high methanol conversion and temperatures as loW as 2300 C. It has the advantageofbeing,contrarytosteamreforming,anexother mic reaction, therefore, minimiZing energy consumption. There is also auto thermal reforming of methanol, Which combines steam reforming and partial oxidation of methanol inaspeci?cratioandaddressesanydraWbackofanexother mic reaction by producing only enough energy to sustain itself. Auto thermal reforming is neither exothermic nor endothermic, and does not require any external heating once the reaction temperature is reached. Despite the aforemen tionedpossibilities,hydrogenfuelcellsmustusehighlyvola tile and ?ammable hydrogen or reformer systems. 20 25 hydrogen carrier for fuel cell vehicles through on-board methanol reformers or can be used directly in DMFC vehicles. Dimethyl ether although gaseous at room tempera ture can be easily stored under modest pressure and used effectivelyinadmixtureWithdieselfuelsandlique?ednatu ral gas (LNG), or used in residential gas mixtures. Methanol is also an attractive liquid fuel for static applica tions. For example, methanol can be used directly as fuel in gasturbinestogenerateelectricpoWer.Gasturbinestypically use natural gas or light petroleum distillate fractions as fuel. Compared to such fuels, methanol can achieve higher poWer output and loWer NO,C emissions because of its loWer ?ame temperature. Since methanol does not contain sulfur, SO2 emissions are also eliminated. Operation on methanol offers the same ?exibility as on natural gas and distillate fuels, and canbeperformedWithexistingturbines,originallydesigned fornaturalgasorotherfossilfuels,afterrelativelyeasymodi ?cation. Methanol is also an attractive fuel since fuel-grade methanol, With loWer production cost than higher purity chemical-grademethanol,canbeusedinturbines.Because thesiZeandWeightofafuelcellisoflessimportanceinstatic applicationsthanmobileapplications,variousfuelcellsother thanPEM fuelcellsandDMFC, suchasphosphoricacid, molten carbonate and solid oxide fuel cells (PAFC, MCFC, andSOFC,respectively),canalsobeused. In addition to use as fuels, methanol, dimethyl ether and derivedchemicalshavesigni?cantapplicationsinthechemi cal industry. Today, methanol is one of the most important feedstock inthe chemical industry. The majority ofthe some 35milliontonsoftheannuallyproducedmethanolareusedto manufacture a large variety of chemical products and mate rials,includingbasicchemicalssuchasformaldehyde,acetic acid,MTBE (althoughitisincreasinglyphasedoutforenvi ronmentalreasons),asWellasvariouspolymers,paints,adhe sives,constructionmaterials,andothers.Worldwide,metha nolisusedtoproduceformaldehyde(38%),methyl-tert-butyl ether (MTBE, 20%) and acetic acid (11%). Methanol is also afeedstockforchloromethanes,methylamines,methylmeth acrylate, and dimethyl terephthalate, among others. These chemicalintermediatesarethenprocessedtomanufacture products such as paints, resins, adhesives, antifreeZe, and plastics. Formaldehyde, produced in large quantities from methanol, is mainly used to prepare phenol-, urea- and melamine-formaldehyde and polyacetal resins as Well as butanediolandmethylenebis(4-phenylisocyanate)MDI foam,Whichisusedasinsulationinrefrigerators,doors,and in car dashboards and bumpers. Formaldehyde resins are predominantly used as adhesives in a Wide variety of appli cations, e.g., manufacture of particle boards, plyWood and otherWoodpanels.Examplesofmajormethanol-derived chemical products and materials produced are listed in FIG. 1. In producing basic chemicals, raW material feedstock con stitutes typically up to 60-70% of the manufacturing costs. Thecostoffeedstockthereforeplaysasigni?canteconomic role and its continued availability is essential. Because of its economicandlongrangeavailabilityadvantages,methanolis considered a potential prime feedstock for processes cur rently utiliZing more expensive feedstock such as ethylene andpropylene,toproducechemicalsincludingaceticacid, acetaldehyde, ethanol, ethylene glycol, styrene, and ethyl benZene, and various synthetic hydrocarbon products. For example, direct conversion of methanol to ethanol can be achieved using a rhodium-based catalyst, Which has been foundtopromotethereductivecarbonylationofmethanolto acetaldehyde With selectivity close to 90%, and a ruthenium catalyst, Which further reduces acetaldehyde to ethanol. U.S. Pat. No. 5,599,638 discloses a simple direct methanol fuelcell(DMFC) toaddressthedisadvantagesofhydrogen fuelcells.Incontrasttoahydrogenfuelcell,theDMFC isnot dependentongenerationofhydrogenbyprocessessuchas electrolysis of Water or reformation of natural gas or hydro carbons. The DMFC is also more cost effective because methanol,asaliquidfuel,doesnotrequirecoolingatambient temperaturesorcostlyhighpressureinfrastructureandcanbe usedWithexistingstorageanddispensingunits,unlikehydro gen fuel, Whose storage and distribution requires neW infra structure. Further, methanol has a relatively high theoretical volumetricenergydensitycomparedtoothersystemssuchas conventional batteries and the HZ-PEM (PEM: proton exchangemembrane)fuelcel.Thisisofgreatimportancefor40 smallportableapplications(celularphones,laptopcomput ers, etc.), for Which small siZe and Weight of energy unit is desired. DMFC offersnumerousbene?tsinvariousareas,includ ingthetransportationsector.Byeliminatingtheneedfora45 methanolsteamreformer,DMFC signi?cantlyreducesthe cost,complexityandWeightofthevehicle,andimprovesfuel economy.A DMFC systemisalsocomparableinitssimplic ity to a direct hydrogen fuel cell, Without the cumbersome problemsofon-boardhydrogenstorageorhydrogenproduc 50 ingreformers.BecauseonlyWaterandCO2 areemitted,emis sionsofotherpollutants(e.g.,NOX,particulatematter,S02, etc.) are eliminated. Direct methanol fuel cell vehicles are expected to be of loW emission (ZEV), and use of methanol fuelcellvehiclesWillgreatlyeliminateairpollutantsfrom 55 vehiclesinthelongterm.Further,unlikeinternalcombustion engine vehicles, the emission pro?le is expected to remain nearlyunchangedovertime.NeW fuelcellmembranesbased onhydrocarbonorhydro?uorocarbonmaterialsWithreduced costandcrossovercharacteristicshavebeendevelopedthat 60 alloW room temperature e?iciency of about 34%. Methanol and dimethyl ether provide a number of impor tantadvantagesastransportationfuels.By contrasttohydro gen, methanol storage does not require any energy intensive proceduresforpressurizationorliquefaction.Becauseitisa 65 liquidatroom temperature, itcanbe easilyhandled, stored, distributed and carried in vehicles. It can act as an ideal 30 35PDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL BIOREFORMING
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