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11 FIG. 2 schematically illustrates the present inventive pro cess,termedtheMETHANOL ECONOMY anditscarbon neutral chemical recycling. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 12 501 ?led Sep. 5, 2007) to provide a 1:2 molar mixture of carbonmonoxideandhydrogen,Whichsubsequentlycan react to produce exclusively methanol. As the reforming of carbondioxideWithmethanegenerateshydrogen,thishydro gencanalsobeusedforthehydrogenationofmethylformate tomethanol inthepreviouslydiscussedembodiments. Methanol produced according to the discussed neW pro cesses can be used for any of the practical mentioned pur poses such as for energy storage and transportation, as a fuel in internal combustion engines or fuel cells, to produce derived fuels (such as dimethyl ether), dimethyl carbonate (andthelike),toproduceethylene,propylene,andrelatedfor converting carbon dioxide formed upon their combustion or byanysourcetomethanol.Suitablecarbondioxidesources 25 can be industrial exhaust streams from hydrocarbon (fossil fuel) burning poWer plants, cement and other industrial plants,naturalgas?elds,undercarbondioxideaccompanies thehydrocarbongases,andthelike,asWellascarbondioxide oftheatmosphereitself.Theuseofthisprocessofconverting 30 carbon dioxide to methanol and/or dimethyl ether and their products Will also lead to a signi?cant reduction of carbon dioxide, a major greenhouse gas, in the atmosphere thus mitigatingglobalWarming. nol formaldehyde and formic acid Which by chemical con versionorphotochemicalorelectrochemicalreductioncan furtherproducemethanol.Theinventionteachesthat,Without separation of the product mixture in a subsequent treatment step, the mixture can be converted exclusively to methanol making the overall process both selective and high yielding. Inanotherembodiment,reductionofcarbondioxidecangive methylformate,Whichissubsequentlyhydrogenativelycon verted exclusively into methanol. In a further embodiment, the chemical reduction of carbon dioxide With carbon or its electrochemicalreductionproducescarbonmonoxide,Which thenisconvertedtomethanolWithutiliZationofneeded hydrogen to form only the desired product. In this embodi US 8,212,088B2 The present invention relates to the e?icient and economi cal conversion of carbon dioxide from ?ue gases of fossil fuel burningpoWerplants,industrialexhaustgases,CO2 accom panying natural gas or from the atmosphere itselfto methanol or dimethyl ether, With their subsequent application for energystorageandtransportation,fuelsforinternalcombus synthetichydrocarbonsandaltheirderivedproductsinclud tionenginesandfuelcells,conversiontosynthetichydrocar ingandnotlimitingsinglecellproteins. bonsandtheirproducts,syntheticproteinsandotherprod ucts. The carbon dioxide to methanol conversion is a permanent, safe and economical alternative to sequestration, (undergroundorundertheseastorage)Whereincarbondiox ide through methanol is converted to useful and essential productsmakingitareneWablegeneralcarbonsourcefor20 fuels,synthetichydrocarbonsandtheirproducts. Thepresentinventionrelatestoe?icientneW andeconomi calWaysofconvertingvariedcarbondioxidesources(both containing high and loW combustions) into methanol. High concentration carbon dioxide sources are those frequently accompanying natural gas in amounts typically form 2 to 35%,thosefrom?uegasesoffossilfuel(coal,naturalgas,oil, etc.)burningpoWerplants,exhaustofcementplants,fermen tation plants and other industrial sources. In one embodiment The present invention discloses an environmentally neutral ande?icientprocessofrecyclingcarboncontainingfuelsand oftheinventioncarbondioxideformedtogetherWithmetha Carbondioxideconversiontomethanolfromthemen 35 tioned generally sources also provides also formic acid and formaldehydebyeitherchemical,photochemicalorelectro menttheinitialreductionofcarbondioxidesigni?cantly(by chemicalreduction.Formicacidandformaldehydethuspro duced, in a subsequent process step, can be subsequently furthersubstantiallyconvertedtomethanol.Theconversion 40 of formaldehyde itselfcan be conducted in the presence of a solidsupportedbasiccatalystoranorganometalliccatalystto fossilfuelburningpoWerplants,fromnaturalgasWells,var give methanol and formic acid, or methyl formate. Alterna ied industrial exhaust gases or from the atmosphere itself, to tively,dimeriZationofformaldehydegivesmethylformate, methanol.Bothcatalytic,photochemicalorelectrochemical Whichuponcatalytichydrogenationyieldsmethanolasthe45 onlyproduct. Carbon dioxide is captured and obtained from mentioned high concentration sources of its generation instead of its release into the atmosphere. Carbon dioxide can, hoWever, alsobeobtainedbyseparatingitfromtheatmosphereitself50 Withasuitableadsorbent(seeco-pendingapplicationSer.No. 11/780,244 ?led Jul. 19, 2007) folloWed by desorption treat ment to release the adsorbed carbon dioxide therefrom. This can be achieved by heating to release the adsorbed carbon dioxide,bytreatingitunderreducedpressureorbyasuitable 55 combination of both. In another embodiment of the invention to utiliZe needed hydrogen only in producing methanol Without Water as by product,carbondioxideis?rstreducedchemically,suchasin itsthermalreactionWithcarbonorelectrochemicallytocar 60 bonmonoxide,Whichissubsequentlycatalyticallyconverted Withhydrogentomethanol. reductionofcarbondioxidecanbeutiliZedWithanyenergy sourceavailable(conventional,alternative,atomic,etc).The environmental and economic bene?ts of reductive chemical conversion of carbon dioxide emission instead of sequestra tionareasigni?cantpartofthepresentinvention.At thesame time,carbondioxideprovidesareneWablesourceofmetha nol (together With dimethyl ether) that can be used for safe energy storage and transportation, production of fuels for intent combustion engine and fuel cells, feedstock for pro ducingsynthetichydrocarbonsandtheirproductsandrelated materials. The use of carbon dioxide based methanol is highly desir able as it can decrease and eventually replace the World’s reliance on fossil fuels. In addition, the reduction in carbon dioxide emissions as Well as the removal of excess carbon dioxidefromtheatmosphereWillassistinreducingglobal Warming and eventual restoring atmospheric conditions to a suitablelevels,thuspreservingtheplanet’sclimateforfuture generations. Thepresentinventionovercomesmany ofthedif?cultiesin economically converting carbon dioxide to methanol. Regardless, hoW energy is generated, any source of energy A furtherroutetomethanolisbasedontheuseofmethane or natural gas as the hydrogen source in the reductive conver sionofcarbondioxide(dryreforming)orusingasuitable 65 combination With steam reforming (Wet reforming) called bi-reforming(seeco-pendingapplicationSer.No.11/850, mustbestoredandtransported.Hydrogenclaimedasthe a third) decreases the overall amount ofhydrogen needed for producingmethanol. The present invention discloses the e?icient and economi cal conversion of carbon dioxide, either from ?ue gases orPDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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