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US 2012/0132538 A1 May 31,2012 natural gas Wells or the atmosphere itself). Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmo sphere. For example, high concentration carbon dioxide sourcesmay frequentlyaccompanynaturalgasinamountsof 5% to50%,existin?uegasesoffossilfuel(e.g.,coal,natural gas,oil,etc.)burningpoWerplants,andhighpuritycarbon dioxide may be exhausted from cement factories, from fer mentersusedforindustrialfermentationofethanol,andfrom themanufactureoffertilizersandre?nedoilproducts.Certain geothermal steams may also contain signi?cant amounts of carbon dioxide. The carbon dioxide emissions from varied industries, including geothermal Wells, may be captured on site. Separation of the carbon dioxide from such exhausts is knoWn. Thus, the capture and use of existing atmospheric carbon dioxide inaccordance With some embodiments ofthe present invention generally alloW the carbon dioxide to be a reneWable and unlimited source of carbon. carbon dioxide to the cell 102. In some embodiments, the carbondioxideisbubbleddirectlyintothecompartment114!) containing the cathode 120. [0031] The ?rst extractor 110 may implement an organic product and/or inorganic product extractor. The extractor 110 is generally operational to extract (separate) one or products of the product mixture (e.g., butanol) from the electrolyte 122.The extractedproductsmay bepresentedthroughaport 126 of the system 100 for subsequent storage and/or con sumption by other devices and/or processes. [0032] Thesecondextractor112mayimplementanoxygen extractor.The secondextractor112 isgenerallyoperationalto extractoxygen(e.g.,O2)byproductscreatedbythereduction of the carbon dioxide and/or the oxidation of Water. The extracted oxygen may be presented through a port 128 ofthe system 100 for subsequent storage and/or consumption by other devices and/or processes. Chlorine and/or oxidatively evolved chemicals may also be byproducts in some con?gu rations, such as in an embodiment of processes other than [0025] ReferringtoFIG.1,ablockdiagramofasystem100 oxygenevolutionoccurringattheanode118.Suchprocesses is shoWn in accordance With a speci?c embodiment of the present invention. System 100 may be utiliZed for the one stageprocessfortheproductionofbutanolfromcarbondiox ideandWater.The system(orapparatus)100generallycom prises a cell (or container) 102, a liquid source 104, a poWer source106,agassource108,a?rstextractor110andasecond extractor112.A productorproductmixturemaybepresented fromthe?rstextractor110.An outputgasmay bepresented from the second extractor 112. [0026] Thecell102maybeimplementedasadividedcell. The dividedcellmay be adividedelectrochemical celland/or adividedphotochemicalcell.Thecell102isgenerallyopera tional to reduce carbon dioxide (CO2) into butanol. The reductiongenerallytakesplacebybubblingcarbondioxide and an aqueous solution of an electrolyte in the cell 102. A cathode 120 in the cell 102 may reduce the carbon dioxide into a product mixture that may include one or more com pounds.Forinstance,theproductmixturemayincludeatleast oneofbutanol,formicacid,methanol,glycolicacid,glyoxal, acetic acid, ethanol, acetone, or isopropanol. In particular implementations,butanolmay accountforlessthanapproxi mately 10% of the total yield of organic compounds in the productmixture. [0027] Thecell102generallycomprisestWoormorecom partments (orchambers) 114a-114b, aseparator(ormem brane) 116, an anode 118, and a cathode 120. The anode 118 may be disposed in a given compartment (e.g., 114a). The cathode 120 may be disposed in another compartment (e.g., 11419) on an opposite side of the separator 116 as the anode 118. An aqueous solution 122 may ?ll both compartments 11411-1141).Theaqueoussolution122may includeWaterasa solvent and Water soluble salts (e.g., potassium chloride (KCl)).Acatalyst124maybeaddedtothecompartment114!) containingthecathode120. [0028] The liquid source 104 may implement a Water source. The liquid source 104 may be operational to provide pure Water to the cell 102. [0029] ThepoWersource106mayimplementavariable voltage source. The poWer source 106 may be operational to generateanelectricalpotentialbetWeentheanode118andthe cathode120.TheelectricalpotentialmaybeaDC voltage. [0030] Thegassource108mayimplementacarbondiox ide source. The source 108 isgenerally operational to provide may includechlorineevolution,oxidationoforganicstoother saleable products, Waste Water cleanup, and corrosion of a sacri?cial anode. Any other excess gases (e.g., hydrogen) createdbythereductionofthecarbondioxideandWatermay be vented from the cell 102 via a port 130. [0033] Inthereductionofcarbondioxidetobutanol,Water may beoxidiZed(orsplit)toprotonsandoxygenattheanode 118 While the carbon dioxide is reduced to the product mix ture at the cathode 120. The electrolyte 122 in the cell 102 may use Water as a solvent With any salts that are Water soluble,includingpotassiumchloride(KCl)andWithasuit able catalyst 124, such as an imidaZole catalyst, a pyridine catalyst, or a substituted variant of imidaZole or pyridine. Cathodematerialsgenerallyincludeanyconductor.HoWever, ef?ciency of the process may be selectively increased by employing a catalyst/cathode combination selective for reduction of carbon dioxide to butanol (and/or other com poundsincludedintheproductmixture).Forcatalyticreduc tionofcarbondioxide,thecathodematerialsmay includeSn, Ag, Cu, steel(e.g.,316 stainlessstel),andalloysofCu and Ni. The materials may be in bulk form. Additionally and/or alternatively, the materials may be present as particles or nanopar‘ticles loaded onto a substrate, such as graphite, car bon ?ber, or other conductor. [0034] Ananodematerialsu?icienttooxidiZeorsplitWater may be used. The overall process may be generally driven by the poWer source 106. Combinations of cathodes 120, elec trolytes 122, and catalysts 124 may be used to control the reactionproductsofthecell102. [0035] Inoneimplementationoftheone-stageprocessof producing butanol from carbon dioxide and Water, a loW yield, loW selectivity for butanol may be obtained using an approximately400mM concentrationofimidaZolecatalyst, KCl electrolyte,anda316 stainlesssteelcathode.Theprocess may proceedviathefolloWingreactions,Withtheheterocy clic catalyst facilitating the reaction similar to NADPH/ NADP+ intheCalvinCycle: 602 pH6)PDF Image | ELECTROCHEMICAL PRODUCTION OF BUTANOL FROM CO2 and H2O
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