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13 future clean energy is exceedingly dif?cult and intrinsically dangerous to store, handle and transport. Its conversion With CO2 to methanol, a convenient liquid and derived products offers a convenient, safe Way of energy storage as Well as a renewable, eventually carbon natural source for synthetic hydrocarbonsandtheirvariedproducts. The energy needed to generate hydrogen for catalytic or electrochemical conversion of carbon dioxide to methanol can be obtained from any available source of energy, such as stilexistingfossilfuelsatomic,solar,Wind,geothermal,etc. Photolytic, thermal, enzymatic, and other means of cleaving of Water to hydrogen are also feasible. CO2 emissionsfromfossilfuelburningpoWerplantsand varied industries can be captured on-site. Separation of CO2 from such industrial exhausts is Well-developed. The major advantageintheneWlydisclosedchemicalrecyclingofthese sources to methanol and derived products isthat carbon diox ide is not released into the atmosphere and serves as reneW able carbon source for fuels and varied essential products. 14 energy storage and transportation materials eliminates many di?icultiesexcessivecostanddangerofusinghydrogenfor such purposes. They are also excellent transportation fuels andconvenientraWmaterialsforproducingsynthetichydro carbons and their related products. The economy, safety and versatility of methanol makes the disclosed recycling of car bon dioxide further desirable. As knoWn in the art, methanol can be easily treated to producevariedderivedcompoundsincludingdimethylether, producedbydehydrationofmethanol,anddimethylcarbon ate, produced by reaction of the methanol by oxidative car bonylation. Methanol and methanol-derived compounds, e.g.,DME andDMC asoxygenatedfuels,canbeeasily blended With gasoline and used in internal combustion or DieselenginesWithonlyminormodi?cations.Forexample, methanol can be added to gasoline up to 85% by volume to obtaincommerciallyviableM20 orM85 fuels.Methanolcan alsobeusedtogenerateelectricityinfuelcells,byeither?rst catalyticallyreformingmethanoltoH2andCO orbyreacting methanoldirectlyWithairinourco-inventeddirectmethanol fuel cell (DMFC) (see U.S. Pat. No. 5,928,806). DMFC greatlysimpli?esthefuelcelltechnologyandmakesitreadily available to a Wide range of applications, including portable mobileelectronicdevicesandelectricitygenerators. US 8,212,088B2 TheseparationanduseofatmosphericCO2alloWschemi calrecyclingofCO2 asareneWableandunlimitedsourceof carbon.CO2 absorptionfacilitiescanbeplacedproximateto a hydrogen production site to enable subsequent methanol synthesis.AlthoughtheCO2 contentintheatmosphereisloW (only0.037%),theatmosphereoffersanabundantandunlim ited supply When CO2 is recycled. For using atmospheric carbon dioxide ef?ciently, CO2 absorption facilities are needed. This can be addressed by using e?icient CO2 absor bentssuchaspolyethyleneimines,polyvinylpyridines,poly includingpolymers,paints,adhesives,constructionmateri 20 25 vinylpyrroles,etc.,onsuitablenano-structuredsolidcarriers (e.g.,activecarbon,polymers,silicaoralumina),WhichalloW absorptionofeventheloWconcentrationofatmosphericCO2 (see co-pending patent application Ser. No. 11/780,244 ?led Jul. 19, 2007). CO2 can also be captured using basic absor bentssuchascalciumhydroxide(Ca(OH)2)andpotassium35 hydroxide (KOH), Which react With CO2 to form calcium carbonate (CaCO3) and potassium carbonate (K2CO3), respectively.CO2 absorptionisanexothermicreaction,Which liberatesheat,andisreadilyachievedbycontactingCO2With anadequatebase.Aftercapture,CO2 isrecoveredfromthe 40 absorbent by desorption, through heating, vacuum (or reduced pressure) or electrochemical treatment. Calcium car bonate,forexample,isthermallycalcinatedtoreleasecarbon dioxide.Asdesorptionisanendothermic,energy-demanding step,theappropriatetreatmentcanbechosentooptimiZe 45 absorption and desorption With the loWest possible energy input.Thus,CO2 canberecycledbyoperationofabsorbing desorbingcolumnsinconvenientcyclesWithmodestheating and/orunderreducedpressuretocausedesorptionofCO2 to takeplace. 50 When methanol, methanol-derived fuels or synthetic hydrocarbonsarecombusted(oxidativelyused),theyrelease CO2 and Water, thus providing the basis for a reversible methanolcycle,thearti?cialversionofthenaturalphotosyn theticrecyclingofCO2.IncontrasttothenonreneWablefossil 55 fuel sources such as oil, gas, and coal recycling carbon diox ide from industrial and natural sources to produce methanol not only addresses the problem of diminishing fossil fuel resources by providing an unexhaustible carbon source, but alsohelpsalleviateglobalWarmingduetogreenhouseeffect,60 Whichissigni?cantlycausedbymankind’sactivitythatis increasingthecarbondioxidecontentintheatmosphere. The effective hydrogenative recycling of carbon dioxide disclosedhereinprovidesneW methods ofproducingmetha nolinanimproved,e?icient,andenvironmentallybene?cial65 Way,WhilemitigatingCO2causedclimatechange(global Warming).Theuseofmethanolandderiveddimethyletheras In addition to being a convenient safe energy storage and transportation material and fuel, methanol and methanol-de rivedDME areusefulstartingmaterialsforvariouschemicals such as formaldehyde, acetic acid, and varied other products 30 als,syntheticchemicals,pharmaceuticals,singlecelproteins andthelike. Methanol and/or dimethyl ether can also be conveniently convertedinasinglecatalyticsteptoethyleneand/orpropy lene(e.g.,inthemethanoltoole?norMTO process),the buildingblocksforproducingsynthetichydrocarbonsand theirproducts. This means that the hydrocarbon fuels and products cur rently derived from oil and natural gas can be obtained from methanol, Which itselfcan be obtained from the chemical recyclingofnaturalorindustrialCO2 sources.A furtheruti liZationofmethanolcanbereadyconversiontoethanolvia hydration of derived ethylene. The overall conversion is Many furtherapplicationsareknoWnandcanbeappliedto carbon dioxide derived methanol. It should be emphasiZed that there is no preference for any particular energy source needed forproducing methanol. All sources, including stil existing fossil fuels alternative sources and atomic energy can be used. Energy once produced must be, hoWever, stored and transported,forWhichmethanolispreferredincontrastto dif?culttohandleandessentiallyhaZardoushydrogen. The improved and ef?cient selective conversion of carbon dioxide, Which can be from atmospheric or industrial exhaust sources, to methanol according to the present invention also providestheneededraWmaterialforWhatisnoWtermedas theMETHANOL ECONOMY process.ThisalloWsconve nient storage and transport of energy as a convenient, safe liquid product that can be used as a fuel in internal combus tion engines or in fuel cells and as a starting material for synthetichydrocarbonsandtheirvariedproducts.The METHANOL ECONOMY processencompassesboththe e?icient direct conversion of stil available natural gasPDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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