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US 2012/0132538 A1 May 31,2012 ELECTROCHEMICAL PRODUCTION OF BUTANOL FROM CARBON DIOXIDEAND WATER CROSS-REFERENCE TO RELATED APPLICATIONS [0001] Thepresentapplicationclaimsthebene?tunder35 U.S.C.§119(e)ofUS. PatentApplicationSer.No.61/417, 938, ?led Nov. 30, 2010 and 61/418,034 ?led Nov. 30, 2010. [0002] Theabove-listedapplicationsareherebyincorpo ratedbyreferenceintheirentirety. FIELD [0003] Thepresentdisclosuregenerallyrelatestothe?eld of electrochemical reactions, and more particularly to meth odsand/orsystemsforelectrochemicalproductionofbutanol from carbon dioxide and Water. BACKGROUND [0004] Thecombustionoffossilfuelsinactivitiessuchas electricitygeneration,transportation,andmanufacturingpro duces billions of tons of carbon dioxide annually. Research sincethe1970sindicatesincreasingconcentrationsofcarbon dioxideintheatmospheremay beresponsibleforalteringthe Earth’s climate, changing the pH of the ocean and other potentially damaging effects. Countries around the World, including the United States, are seeking Ways to mitigate emissions of carbon dioxide. [0005] A mechanismformitigatingemissionsistoconvert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. Ifthe carbon dioxide is con vertedusingenergyfromreneWablesources,bothmitigation of carbon dioxide emissions and conversion of reneWable energy into a chemical form that can be stored for later use Willbepossible. [0006] HoWever,the?eldofelectrochemicaltechniquesin carbondioxidereductionhasmany limitations,includingthe stability of systems used in the process, the ef?ciency of systems, the selectivity of the systems or processes for a desired chemical, the cost of materials used in systems/pro cesses,theabilitytocontroltheprocesseseffectively,andthe rateatWhichcarbondioxideisconverted.Inparticular,exist ing electrochemical and photochemical processes/systems have one or more of the folloWing problems that prevent commercialization on a large scale. Several processes utiliZe metals,suchasrutheniumorgold,thatarerareandexpensive. In other processes, organic solvents Were used that made scaling the process di?icult because of the costs and avail ability of the solvents, such as dimethyl sulfoxide, acetoni trile, and propylene carbonate. Copper, silver and gold have been found to reduce carbon dioxide to various products, hoWever, the electrodes are quickly “poisoned” by undesir able reactions on the electrode and often cease to Work in less than an hour. Similarly, gallium-based semiconductors reduce carbon dioxide, but rapidly dissolve in Water. Many cathodesproduceamixtureoforganicproducts.Forinstance, copper produces a mixture of gases and liquids including carbonmonoxide,methane,formicacid,ethylene,andetha nol.Suchmixturesofproductsmake extractionandpuri?ca tionoftheproductscostlyandcanresultinundesirableWaste products that must be disposed. Much of the Work done to dateoncarbondioxidereductionisinef?cientbecauseofhigh electrical potentials utiliZed, loW faradaic yields of desired products, and/or high pressure operation. The energy con sumedforreducingcarbondioxidethusbecomesprohibitive. Manyconventionalcarbondioxidereductiontechniqueshave very loW rates of reaction. For example, in order to provide economic feasibility, a commercial system currently may requiredensitiesinexcessof100milliamperespercentimeter squared(mA/cm2),Whileratesachievedinthelaboratoryare ordersofmagnitudeless. SUMMARY [0007] Amethodforelectrochemicalreductionofcarbon dioxidetoproducebutanolmay include,butisnotlimitedto, steps (A) to (D). Step (A) may introduce Water to a ?rst compartment of an electrochemical cell. The ?rst compart ment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The secondcompartmentmay includeasolutionofanelec trolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential betWeen the anode and the cathode in the electrochemical cell suf?cient for the cathode to reduce the carbondioxidetoaproductmixture.Step(D)mayseparate butanolfromtheproductmixture. [0008] Anothermethodforelectrochemicalreductionof carbondioxidetoproducebutanolmay include,butisnot limitedto,steps(A)to(F).Step(A)may introduceWatertoa ?rst compartment of a ?rst electrochemical cell. The ?rst compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the ?rst electro chemicalcell.The secondcompartmentmay includeasolu tion ofan electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential betWeen the anode and the cath ode in the ?rst electrochemical cell su?icient for the cathode to reduce the carbon dioxide to an intermediate product mix ture.Step(D)may separateatWo-carbonintermediatefrom theintermediateproductmixture. Step (E)may introducethe tWo-carbon intermediate to a second electrochemical cell. Thesecondelectrochemicalcellmayincludeananodeina ?rst cell compartment and a cathode in a second cell com partment. The cathode may reduce the tWo-carbon interme diatetoaproductmixture.Step(F)may separatebutanolfrom theproductmixture. [0009] A systemforelectrochemicalreductionofcarbon dioxidetoproducebutanolmay include,butisnotlimitedto, a?rstelectrochemicalcellincludinga?rstcellcompartment, an anode positioned Within the ?rst cell compartment, a sec ond cell compartment, a separator interposed betWeen the ?rst cell compartment and the second cell compartment, and a cathode and a catalyst positioned Within the second cell compartment. The system may also include a carbon dioxide source, Where the carbon dioxide source is coupled With the second cell compartment and is con?gured to supply carbon dioxide to the cathode for reduction of the carbon dioxide to an intermediate product mixture. The system may also include an extractor con?gured to separate a tWo-carbon intermediatefromtheproductmixture.The systemmay fur ther include a second electrochemical cell con?gured to receive the tWo-carbon intermediate. The second electro chemicalcellmay includea?rstcellcompartment,ananode positioned Within the ?rst cell compartment, a second cell compartment, a separator interposed betWeen the ?rst cell compartment of the second electrochemical cell and the sec ondcellcompartmentofthesecondelectrochemicalcell,and a cathode positioned Within the second cell compartment of the second electrochemical cell. The cathode of the secondPDF Image | ELECTROCHEMICAL PRODUCTION OF BUTANOL FROM CO2 and H2O
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