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US 7,906,559B2 56 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. Theusefulnessofmethanolhasledtodevelopmentofother reforming processes, for example, a process knoWn as oxida tive steam reforming, Which combines steam reforming, par tialoxidationofmethanol,usingnovelcatalystsystems.Oxi dativesteamreformingproduceshighpurityhydrogenWith ZeroortraceamountsofCO, athighmethanolconversionand temperatures as loW as 2300 C. Ithas the advantage ofbeing, contrary to steam reforming, an exothermic reaction, there foreminimizingenergyconsumption.Thereisalsoautother malreformingofmethanol,Whichcombinessteamreforming and partial oxidation of methanol in a speci?c ratio and addresses any draWback of an exothermic reaction by pro ducing only enough energy to sustain itself. Autothermal reforming is neither exothermic nor endothermic, and does notrequireanyexternalheatingoncethereactiontemperature isreached.Despitetheaforementionedpossibilities,hydro 20 gen fuel cells must use highly volatile and ?ammable hydro gen or reformer systems. Regardless,ourdirectmethanolfuelcell(DMFC) thatWe haveinventedtogetherWithCaltech’sJPL utiliZingmethanol has signi?cant advantages over reformer based fuel cells. 25 U.S. Pat. No. 5,599,638, of Which We are coinventors, discloses a simple direct methanol fuel cell (DMFC) to addressthedisadvantagesofhydrogenfuelcells.Incontrast toahydrogenfuelcell,theDMFC isnotdependentongen erationofhydrogenbyprocessessuchaselectrolysisofWater30 orreformationofnaturalgasorhydrocarbons.TheDMFC is also more cost effective because methanol, as a liquid fuel, does not require cooling at ambient temperatures or costly high pressure infrastructure and can be used With existing storageanddispensingunits,unlikehydrogenfuel,Whose 35 storageanddistributionrequiresneW infrastructure.Further, methanol has a relatively high theoretical volumetric energy density compared to other systems such as conventional bat teriesandtheHZ-PEM fuelcell.Thisisofgreatimportance forsmallportableapplications(cellularphones,laptopcom 40 puters,etc.),forWhichsmallsiZeandWeightofenergyunitis desired. DMFC offersnumerousbene?tsinvariousareas,includ ing the transportation sector. By eliminating the need for a methanolsteamreformer,DMFC signi?cantlyreducesthe45 cost,complexityandWeightofthevehicle,andimprovesfuel economy.A DMFC systemisalsocomparableinitssimplic ity to a direct hydrogen fuel cell, Without the cumbersome problemsofon-boardhydrogenstorageorhydrogenproduc ingreformers.BecauseonlyWaterandCO2areemitted,emis 50 sionsofotherpollutants(e.g.,NOX, PM, S02,etc.)areelimi nated. Direct methanol fuel cell vehicles are expected to be loW emission vehicles (ZEV), and use of methanol fuel cell vehicles offers to greatly eliminate air pollutants from vehiclesinthelongterm.Further,unlikeICEvehicles,the55 emissionpro?leisexpectedtoremainnearlyunchangedover time. NeW fuel cell membranes based on hydrocarbon or hydro?uorocarbonmaterialsWithreducedcostandcrossover characteristicshavebeendevelopedthatalloWroomtempera tureef?ciencyof~34%. 60 MethanolandDMEasindicatedprovideanumberof important advantages as transportation fuels. Contrary to hydrogen, methanol storage does not require any energy intensive procedures for pressurization or liquefaction. Becauseitisaliquidatroomtemperature,itcanbeeasily 65 handled, stored, distributed and carried in vehicles. It can act as an ideal hydrogen carrier for fuel cell vehicles through on-board methanol reformers or can be used directly in DMFC vehicles.DME althoughgaseousatroomtemperature canbeeasilystoredundermodestpressureandusedeffective inadmixtureWithdieselfuelsandCNG, orusedinresidential 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-grade methanol, can be used in turbines. Because thesiZeandWeightofafuelcellisoflessimportanceinstatic applicationsthanmobileapplications,variousfuelcellsother thanPEM fuelcellsandDMFC, suchasphosphoricacid, molten carbonate and solid oxide fuel cells (PAFC, MCFC, and SOFC, respectively), can also be used. Inadditiontouseasfuels,methanol,DME andderived chemicals have also signi?cant applications in the chemical industry. Today, methanol is one of the most important feed stock in the chemical industry. Most of the some 35 million tons of the annually produced methanol is used to manufac turealargevarietyofchemicalproductsandmaterials, includingbasicchemicalssuchasformaldehyde,aceticacid, MTBE (althoughitisincreasinglyphasedoutforenviron mental reasons), as Well as various polymers, 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 chemical intermediates are then processed to manufacture productssuchaspaints,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 butanediol and methylene bis(4-phenyl isocyanate) 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 other Wood panels. Examples of major methanol-derived chemicalproductsandmaterialsproducedareshoWninFIG. 1. Inproducingbasicchemicals,raWmaterialfeedstockscon stitutetypicallyup to60-70% ofthemanufacturingcosts.The cost of feedstock therefore plays a signi?cant economic role anditscontinuedavailabilityisessential.Becauseofitseco nomic and long range availability advantages methanol is considered a potential prime feedstock for processes cur rently utiliZing more expensive feedstocks such as ethylene and propylene, to produce chemicals including acetic acid, 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 found to promote the reductive carbonylation of methanol to acetaldehydeWithselectivitycloseto90%,andaruthenium catalyst, Which further reduces acetaldehyde to ethanol. Another feasible Way to produce ethanol from methanolPDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL
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