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15 resourcestomethanol ordimethylether(asdisclosedinUs. patentapplicationSer.No.11/402,051?ledApr.12,2006,the entire content of Which is incorporated herein by reference thereto) With ?rst producing syn-gas as Well as the presently disclosed reductive chemical conversion of carbon dioxide. TheconceptoftheMETHANOL ECONOMY processpre sentssigni?cantadvantagesandgreateconomicpossibilities. IntheMETHANOL ECONOMY process,methanolisused as (1) convenient energy storage medium, Which alloWs con venientandsafestorageandhandling;(2)readilytransported anddispensedfuel,includingforinternalcombustionengines and methanol fuel cells; and (3) feedstock for synthetic hydrocarbonsandtheirproductscurrentlyobtainedfromoil and gas resources, including polymers and even single cell proteins, Which can be used for animal feed or human con sumption. The environmental bene?ts obtained by disclosed chemicalrecyclingofcarbondioxideresultsinmitigatingthe global Warming to ensure the Well being of future genera tions. Asmethanolisreadilydehydratedtodimethylether,the20 disclosed conversion of carbon dioxide to methanol is also adaptable to produce dimethyl ether for fuel and chemical applicationsaspreviouslynoted. The disclosed neW ef?cient production and recycling of methanolfromindustrialornaturalcarbondioxidesources, or even from the air itself, provides the needed raW material for replacing the diminishing fossil fuel through the METHANOL ECONOMY process.Theconversionofcar bon dioxide to methanol requires signi?cant energy, Which can be provided by any energy source including offpeak 30 electricpoWeroffossilfuel(e.g.,coal)burningpoWerplants, atomic energy or any alternative energy sources (solar, Wind, geothermal,hydro,etc.).Asindicated,energygeneratedmust be conveniently stored and transported. The conversion of CO2tomethanolalloWsstorageandtransportationofenergy 35 as a liquid product in an economic and safe Way much more suitable than highly volatile hydrogen gas. Methanol and/or dimethyl ether are e?icient fuels for internal combustion engines or direct oxidation methanol fuel cells (DMFC as WellasraWmaterialsforole?ns,synthetichydrocarbonsand40 other products). The present invention signi?cantly extends the scope of the utiliZation of carbon dioxide for the produc tion of methanol and/or dimethyl ether from natural or indus trial sources, even to the air itself. Usingthepreviouslydescribedprinciplesoftheinvention, 45 aneW andinventiveWay isnoW disclosedtorenderfossilfuels and their products reneWable on the human time scale and environmentallycarbonneutraloncombustion,alloWingthe mitigationofexcesscarbondioxideandthepreventionofits buildupintheatmospheretocounteracttheresultantglobal Warming effects, through the use of neW useful fuels and productsandtherecyclingoftheemissionsfromthecombus tionofsuchfuelsandproducts. The present invention describes a process for effective environmentalrecyclingofcarbondioxideandmethanol. Without being limiting, this process ensures extraction of carbon dioxide, its conversion to methanol and/or dimethyl ether, energy production obtained from the use of methanol and/ordimethylether,furtherextractionofthecarbondioxide bi-productobtainedintheenergy-generatingmethanoland/ 60 ordimethyletherreaction,andrepeatingadesirednumberof times in cycles the above sequence of steps. Even ifinitial, temporary carbon dioxide storage Would be affected by sequestrationtodevelop,suchstoredCO2 cansubsequently convenientlyusedtoproducemethanol. In these embodiments, the carbon dioxide can be obtained from any available source disclosed herein, such as, Without 16 beinglimiting.TheseincludehighCO2containingemissions ofpoWerplantsburningfossilfuels,fermentationprocesses, calcination of limestone, other industrial or natural sources, asWellaseventheloWCO2 contentoftheatmosphere.Inany embodiment, the methanol in the present invention can be obtained from any available source, such as, Without being limiting, the processes described in the present application, alternative agricultural and live sources, or any other indus trialornaturallyoccurringprocess. In a preferred embodiment of the invention, the carbon dioxide source is an exhaust stream from fossil fuel burning poWer or industrial plant, or a source accompanying natural gas.A non-limitingutilityofthepresentinventionisincon nection With coal and other fossil fuel burning poWer plants and industries producing large amounts of carbon dioxide. After obtaining and separating from the source, and With draWing from sequestration storage facilities, the carbon dioxide is then subjected to hydrogenative chemical conver siontoformmethanol,and/or,insubsequentreactionorreac tions,tofurtherformdimethyletherorothercarbonbased fuels and products. The energy required for the process can come from any suitable energy source, including, but not limitedto,excessenergyfromfossilburningpoWerplantsin off peak use periods, alternative energy sources, atomic energysources,etc.VariousenergysourcesareWellknoWnin theart.On combustionofthecarbonbasedfuelsandprod ucts,thereleasedcarbondioxidebi-productisthenconverted again to methanol, as described above, and the cycle is repeated a desired number of times. In an alternative embodiment of the invention, the carbon dioxide source isthe airofour atmosphere. The carbon diox ideisseparatedandabsorbedbyusingmeanseitherdisclosed intheartand/ordescribedinthepresentapplication,anditis then recycled, as described in the foregoing sections. EXAMPLES ThefolloWingexamplesillustratebutnotlimittheutilityof thepresentprocess.TheyarebasedontheuseofknoWn suitable or modi?ed chemical reactions that are applied to the processes of the invention. Example 1 Carbon dioxide inWater isknoWn tobe electrochemically reduced to formic acid and formaldehyde With methanol formed in smaller amounts While avoiding methane forma tioninaqueousmediaoverSn,Pb,In,Zn,Au,Cu,Pdand relatedelectrodesatroom temperatureintherangeof40-90% currente?iciency. The above mentioned product mixture containing formic acid and formaldehyde When passed over a supported basic catalystinatubereactorattemperaturesbetWeen100and 3000C.formingmethanolandmethylformateinoverallyield of 40 to 50%. Example2 Carbon dioxide is reacted With a suitable carbon source (suchascharcoalandthelike)attemperaturesof550to900° C. to produce carbon monoxide in What is called the Boud ouardreaction.CO thenisreactedWithmethanoltogive methylformateandcatalyticallyhydrogenativeconvertedto produce a doubled amount of methanol. US 8,212,088B2 25 50 55 65PDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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