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11 the scope of our invention to adjust the amounts of methane, CO2 andH20 toachievethereactionconditionsofthebi reformingprocess. Our inventionrepresentan ef?cientneW method toconvert carbon dioxide With methane (natural gas) to methanol an/or dimethyletherusingaspeci?cgasmixtureoftWoreforming processes i.e steam (H20) and dry (CO2) reforming to pro ducea1:2molarratioofCO andH2(inaprocesscalled Bi-reformingTM) for the exclusive production of methanol With no production or release of CO2 to the atmosphere or unWantedby-productformationusingupcostlyhydrogento produceWater. The needed individual processes are: A.2CH4+ZHZO—>2CO+6H2Steamreforming B.CH4+CO2—>2CO+2H2dryreforming C.3CH4+ZHZO+CO;—>4C0+8H;overallbi-reforming W TheprocesscanbepracticedbycarryingoutstepsA andB separately.TheproductsofreformingofstepsA andB are mixedbeforebeingintroducedintothemethanolproducingC step.ThetWoreformingsteps,hoWever,canalsobecombined into a single one. In any of the embodiments, no carbon dioxideisproducedtobesequesteredorreleasedintothe atmosphere.FurtherthecompleteutiliZationofCH4 (natural gas) to methanol Without producing any by-product repre sentsasigni?canteconomicalandenvironmentaladvantages. This is in contrast to the tri-reforming process of methane in Whichasynergeticcombinationofdryreforming,steam35 reforming and partial oxidation or methane is carried out in a single step, but produces by-products (CO2 and H20) in the oxidation step representing a signi?cant economic disadvan tageandenvironmentalproblem.Ourpresentinventionusing thedisclosedbi-reformingapproachalloWsWellcontrolled,40 high selectivity and yield conversions of carbon dioxide to methanol Without any by-product and the di?iculties and disadvantagesconnectedusingconcurrentpartialoxidation resulting in undesirable excess carbon dioxide and Water. As steam used in the bi-reforming process is readily internally recycledtheinventionalsoisadaptablefortheproductionof dimethyl ether from CO2 and methane With no by-product (H2O or CO2) formation in the overall process Which can be representedas 50 The aforementioned bi-reforming process thus can also be advantageously used for the preparation of dimethyl ether (DME) Without by-product Water formation, as isthe case in 55 thepresentlyuseddehydrationofmethanol.UntilnoW knoWn reactionofCO2 Withmethane (dryreforming)Was notitself suitabletoproducedimethylether,asitgivesonlya1:1molar mixtureofCO andH2 60 What enables the noW discovered neW Way to convert methaneandCO2 todimethyletheristheuseofbi-reforming WithrecyclingofformedWaterintothebi-reformingstep,65 preferentially by Way a suitable solid acid catalysts such as Na?on-H. 12 TheDME formingprocessofCO2methanethusgives exclusivelyDME. The aforementioned bi-reforming of CO2 With methane can also be directly applied to natural gas itselfto produce methanoland/orDME accordingto 3CnH(2n+2)+(3n—1)H2O+CO2—>(3n+1)CO+(6n+2) H2—>4nCH3OH effected by either in separate steps or in a single step With proper selection of mixing to obtain the needed 1:2 CO:H2 molarmixture. A preferredneWlydiscoveredcatalyst,Whichispartofour inventionfortheCO2bi-reformingprocessstepisVZO5and NiO deposited on suitable high surface are a silica carrier, such as nano-structured fused silica i.e. SiO2(V2O5)NiO operating preferably at 800-950° C. Separate steam reform ingstepistypicallyperformedusingnickelcatalystsattem peraturesof800-10000C.accordingto US 7,906,559B2 20 25 30 bi-reforming process can ?nd utility in numerous applica tions, either alone, or upon subsequent conversion to other products.Withoutbeinglimiting,methanolDME andtheir derived products can be used as synthetic ICE fuels, effective dieselfuels(includingmixingvariedamountsofDMEdim ethyletherWithconventionaldieselfuel),gasoline-methanol mixed fuels (prepared by adding methanol to gasoline With thefuelhavingaminimum gasolinecontentofatleast15% by volume). Without being limited as to other uses, methanol and/ordimethyletherareconvenientenergystorageand transportationmaterialsinordertominimiZeoreliminatethe disadvantages or dangers inherent in the use and transporta tionofLNG orLPG.DME isalsoaconvenienthouseholdgas to replace natural gas. They are also convenient raW materials for producing ole?ns (ethylene, propylene etc.) synthetic hydrocarbons,theirproductsandmaterials,evenforprepar ing single cell proteins for human or animal consumption. Methanol or dimethyl ether produced via the disclosed 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 1ngs, FIG. 1 shoWs illustrative examples of methanol-derived chemicalproductsandmaterials;and FIG. 2 schematically illustrates the general concept of the inventive process termed the Methanol Economy process by inventorGeorgeOlah. DESCRIPTION OF THE PREFERRED EMBODIMENTS The inventionrelatestoaneW, ef?cientprocess ofconver sionofanycarbondioxidesource,amethanesourcesuchas natural gas, coalbed methane, methane hydrate or any other sources to methanol and/or dimethyl ether With any hydrogenPDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL
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