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Whichthermaldecompositionofmethaneproduceshydrogen andsolidcarbon.ThegeneratedhydrogenisthenreactedWith CO2 toproducemethanol.Thisprocessisadvantageousover methanesteamreformingforrequiringrelativelylessenergy, about 9 kcal for producing one mole of hydrogen, and for producing a solid byproduct (carbon) that can be more easily handled,storedandused,comparedtoCO2 emissionsgener atedbymethane steamreformingorpartialoxidation.HoW ever,thethermaldecompositionofmethanerequiresheating itto temperatures of above 800° C. and gives only relatively loW yield of hydrogen. The process, in any case, requires substantialdevelopmentforcommercialapplication. Ifmethanol isto be produced on a large scale from recy cling carbon dioxide, such a process Will be based on the abundant supply of carbon dioxide in the atmosphere and in industrialexhaustsoffossilfuelpoWerburningpoWerplants and cement plants. ItWould atthe same time also mitigate the greenhouseeffectofCO2 thatiscausinginasigni?cantWay theman causedglobalclimatechange (i.e.,globalWarming). The present invention noW provides such a process to obtain thesebene?ts.Furthermore,Whileitisofcriticalimportance 20 tocurtailexcessiveman causedcarbondioxideemissionsinto the atmosphere, this alone Will not be su?icient to reverse the damage that has already occurred. Thus, in addition to use every method for reducing the emission of excess carbon dioxideduetohumanactivitiesintotheatmosphere,itWould 25 beofgreatbene?ttoalsobeabletoremoveandrecycleexcess carbon dioxide from the atmosphere to mitigate and reverse the harmful problem of carbon dioxide buildup in the atmo sphere. Furthermore,naturalfossilfuelresources(petroleumoil,30 natural gas, coal, etc.) and their products are continuingly being depleted. Humankind is greatly dependent on these carbonbasedfossilfuelsandfuelproducts,andtheirongoing depletion from the environment results in a number of sig ni?cantproblemsandchallenges.Uponhumanuse,fuelsand 35 fuel products are not environmentally reneWed on a human timescaleduration,asthecombustionproductscarbondiox ideandWaterdonotrecyclebacktoformneW fuels.Further more, carbon dioxide is a greenhouse gas, Which When pro ducedinlargevolumescontributestoglobalWarmingand40 environmental calamities. Photosynthesisinature’s Way of recycling carbon diox ide,alloWsplantstogroWbytakinginandconvertingcarbon dioxide and Water into carbohydrates in the presence of sun light.Photosynthesicconversionofcarbondioxidefrom45 plantlifetofossilfuels,hoWever,requiresthepresenceofvast territories of forest or agricultural land and energy, and the process is extremely sloW (in the magnitude of millions of years). Presently,theonlyknoWnWaytomitigatethecarbondiox 50 ideemissioninfuelgasesoffossilfuelburningpoWerplants and other emission is by Way of separating, collecting, and subsequentlysequesteringcarbondioxideinoldoil?eldsub terranean geological formations or at the bottom of the seas. Sequestrationis,hoWever,acostlyprocess,asWellasonethat 55 has only temporary mitigating effects due to the potential danger that dynamic geological events could lead to cata strophicreleaseoflargeamountsofsequesteredcarbondiox ide,andtoareneWedenvironmentalhaZard,eg fromthe suffocatingeffectsofthisdangerousgas.Itisagoalofthe 60 present invention to ?nd a practical and economical solution to overcome these problems. 10 carbon dioxide from industrial or natural sources, as Well as from the air itselfinto methanol dimethyl ether and derived products.Thismethodcomprisesseparatingthecarbondiox ide from any available source containing same and producing methanolbyreducingthecarbondioxidethusobtainedunder conditions su?icient to produce methanol; utiliZing the methanol thus produced under conditions su?icient to gener ate upon its combustion energy and to chemically absorbing and recycling formed carbon dioxide in a carbon neutral cycle. The carbon dioxide obtained from such sources istypically convertedtomethanolbycatalytic,photochemicalorelectro chemical hydrogenation. The conversion to methanol, hoW ever,formsareactionmixturealsocontainingformicacidand formaldehyde. These can be Without separation of the reac tionmixture,inasubsequenttreatmentstepconductedunder conditions su?icient to produce formaldehyde and formic acidthemselvesconvertedtomethanolusingmodi?cationsof theso-calledCaniZZaro-Tischenkoreactions.Convertingthe formaldehyde With co-formed formic acid as a hydrogen source is also feasible, Without separation of the reaction mixture, into methanol, and by reacting some of the formic acid With methanol to form methyl formate, folloWed by hydrogenatingthemethylformateunderconditionssuf?cient to form methanol. The hydrogen needed for the hydrogena tion of methyl formate can be obtained from electrolysis of Water, by decomposing at least some of the formic acid from the reaction mixture or by the reaction of methane With car bondioxide(dryreforming). The available source of carbon dioxide is preferably an exhaust stream from a fossil fuel burning poWer or other industrial plants, or a natural source accompanying natural gas. These available sources Would otherWise be released into the atmosphere. The utiliZation of the exhaust stream as a source for chemical recycling avoids emitting the carbon dioxide into the atmosphere. The available source of carbon dioxidemay alsotheairofouratmosphereWiththecarbon dioxideobtainedbyabsorbingatmosphericcarbondioxide onto a suitable adsorbent folloWed by treating the adsorbent toreleasetheadsorbedcarbondioxidetherefrom.By remov ingandrecyclingcarbondioxidefromtheatmospherepro vides a source that is inexhaustible. Suitably, the adsorbent is treatedbysu?icientheatingorissubjectedtosuf?cient reduced pressure to release the adsorbed carbon dioxide. The methanol that is produced can also be dehydrated under conditions su?icient to produce dimethyl ether. The dimethyl ether can be used as a suitable fuel; to be used as a substituteforDieselfuelorhouseholdgas.Combustionof such fuel Will of course generate carbon dioxide, but as car bon dioxide can be recovered and recycled for use in the production of methanol and or dimethyl ether this creates againanenvironmentallycarbonneutralcycle.Themethanol or dimethyl ether as indicated can be also utiliZed as conve nientenergystorageandtransportationmaterialsintheafore mentionedcycles. BRIEF DESCRIPTION OF THE DRAWINGS The features and bene?ts of the invention Will become more evident from revieW of the folloWing detailed descrip tionofillustrativeembodimentsandtheaccompanyingdraW ings,Wherein: FIG.1shoWsknoWnexamplesofmethanol-derivedchemi calproductsandmaterials;and SUMMARY OF THE INVENTION Our invention relates to various embodiments of an envi ronmentally carbon neutral use of utiliZing and recycling 65 US 8,212,088B2PDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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