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US 2007/0161095A1 Jul.12,2007 BIOMASS FUEL SYNTHESIS METHODS FOR INCREASED ENERGY EFFICIENCY CROSS-REFERENCE TO RELATED APPLICATIONS [0001] ThisapplicationclaimsprioritytoUS.Provisional Patent Application Ser. No. 60/767,403, ?led on Mar. 25, 2006, for “Biomass Fuel Synthesis Methods for Increased Energy Efficiency.” This application is also a continuation in-partofUS. patentapplicationSer.No. 11/306,911,?led on Jan. 16, 2006, Which claims priority to US. Provisional Patent Application Ser. No. 60/593,485, ?led on Jan. 18, 2005, for “High E?iciency Absorption Heat Pump and Methods of Use.” This application is also a continuation in-partofUS. patentapplicationSer.No. 11/309,025,?led onJun.12,2006,WhichclaimsprioritytoUS. Provisional Patent Application Ser. No. 60/595,167, ?led on Jun. 13, 2005, for “Nano-Ionic Liquids and Methods of Use.” Each of these applications is incorporated herein by reference in itsentirety. FIELD OF THE INVENTION [0002] Theinventionisdirectedtothesynthesisofbio mass fuels utilizing supercritical ?uids and ionic liquids and a range of supercritical process methods that enable high energy ef?ciency conversion and transformation to alterna tive fuels including biofuels. BACKGROUND [0003] Celluloseethanolrequiresmoreadvancedpretreat ment methods because the sugar carbon componentsi cellulose and hemicelluloseiare much more di?icult to hydrolyze economically into fermentable sugars. After the cellulose and hemicellulose have been sacchari?ed, the remainder of the ethanol production process is similar to grain-ethanol.Hydrolysis(sacchari?cation)breaksdoWnthe hydrogen bonds in the hemicellulose and cellulose fractions into their sugar components: pentoses and hexoses. These sugars can then be fermented into ethanol. [0004] Ionicliquids“IL”canaffectdissolutionofcellu loses from a variety of sources including plants, silk ?broin, and Wool With no degradation of the solutes. In the case of cellulose, the solvation mechanism is proposed to involve the interaction of the IL chloride ions, Which are non hydratedandinaconcentrationofapproximately20Weight %. [0005] High-resolution13CNMR studiesofcelluloseand cellulose oligomers dissolved in the ionic liquid (IL) 1-bu tyl-3-methylimidazolium chloride ([C4mim]Cl) shoW that the b-(1A4)-linked glucose oligomers are disordered in this medium and have a conformational behavior Which parallels the one observed in Water, and thus, reveal that the polymer is disordered IL solution as Well. [0006] Thechlorideionspresentin[C4mim]Clsolutions, Which are non-hydrated and in a concentration of approxi mately 20 Wt %, effectively break the extensive hydrogen bonding netWork of the polysaccharide by interacting With itshydroxylgroups,therebypromotingcellulosedissolution With no apparent degradation of the glycosidic bonds. In ordertobetterunderstandhoW [C4mim]Cl effectscellulose dissolution,theconformationalbehaviorofthepolysaccha ride upon solvation by this IL needs to be investigated. [0007] ILsarecapableofdissolvingcarbohydratesrang ingfromsimplesugarstopolysaccharides.Some ofthebest results in this regard have been obtained With [C4mim]Cl. As recently shoWn, the nonhydrated chloride ions present in solutionsofthisILsolvatecarbohydratesbyforminghydro gen bonds With their hydroxyl groups. For example, cellu losesolutionsinconcentrationsofupto25Wt% canbe obtainedWith[C4mim]Cl. [0008] Ionicliquidsincluding1-butyl-3-methylimidazo liumchloride(“Ionicliquidsasgreensolvents:Engineering neW bio-based materials” by Richard P. SWatloski, John D. Holbrey, Scott K. Spear, and Robin D. Rogers, Department of Chemistry and Center for Green Manufacturing, The University of Alabama, Tuscaloosa, Ala. 35487); “Use of ionicliquidsinthestudyoffruitripeningbyhigh-resolution CNMR spectroscopy:‘green’solventsmeetgreenbananas” byDiegoA.Fortetal.received(inColumbia,Mo.,USA) 23 Oct. 2005, ?rst published as an Advance Article on the Web 19 Jan. 2006 that banana pulps at any ripening stage can be completely dissolved in solvent systems based on the ionic liquid (IL) 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl). [0009] JoseIborraoftheUniversityofMurciainSpain and co-Workers further used a combination of supercritical carbon dioxide and ionic liquids to help an enzyme trans form some organic molecules. Unfortunately, enzymes typi cally don’t Work Well in carbon dioxide. So Iborra’s group devised a tWo-phase reactor in Which the organic starting materials are dissolved in supercritical carbon dioxide and passed through a chamber containing a yeast enzyme dis solved in an ionic liquid. [0010] A Wide range of pretreatment processes exist includingthefolloWing: [0011] US.Pat.No.6,267,309for“MunicipalsolidWaste processing facility and commercial ethanol production pro cess” to Chielfalo, et al. utilizes concentrated sulfuric acid as a means of solubilizing the cellulose Within a pretreatment step. [0012] US.Pat.No.5,135,861for“Methodforproducing ethanol from biomass” to Pavilon utilizes a mixture of biomass and Water that subsequently produces carbon diox ide “CO2” as a byproduct. The carbon dioxide byproduct from the initial fermentation product subsequently aids the catalytic hydrolysis conversion of the biomass. The ’861 patent furthermore limits the operating pressure Well beloW the supercritical pressure of C02. [0013] UnitedStatesPatentApplicationNo.20020164731 for “Process for the simultaneous production of xylitol and ethanol” to Eroma, Olli-Pekka et al. utilizes traditional pretreatment processes for biomass hydrolysates selected from the group consisting of direct acid hydrolysis of said biomass,enzymaticprehydrolysateobtainedbyprehydroly sis of said biomass With steam or acetic acid, acid hydrolysis ofprehydrolysateobtainedbyprehydrolysisofsaidbiomass With steam or acetic acid, autohydrolysis using Water or steam, and a sulphite pulping process. [0014] US.Pat.No.5,711,817for“Methodforthecon tinuousconversionofcellulosicmaterialtosugar”toTitmas utilizes gravity as a means of increasing the cellulosic material liquid stream (a.k.a. biomass slurry) pressure in order to increase the thermodynamic ef?ciency.PDF Image | United States Patent Application Publication US2007 0161095A1
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