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US 2007/0161095A1 Jul.12,2007 nitrate, iron (Il),manganese (IV), sulfate, carbon dioxide, or in some cases the chlorinated solvents such as tetrachlo roethene (PCE), trichloroethene (TCE), dichloroethene (DCE), and vinyl chloride (VC). [0086] Theterm“processintensi?cationmixer”isde?ned as the utilization of micromixing, particularly With super critical ?uids, to achieve high mass transfer. Supercritical ?uidsincludegasessuchascarbondioxide,methane,metha nol, ammonia, ethanol, butanol, and hydrogen. The devices includehydrodynamiccavitationdevices,spinningdisk,and spinning tube in tube. the enZymatic and/or catalytic additives. The resulting bio mass solution is further processed utiliZing the preferred processintensi?cationmixer,includingthedepictedhydro dynamic cavitation device 50 that has an additional bene?t of creating very high instantaneous pressures during the collapseofbubblesthuscreatingcavitation.A Widerangeof equipment is knoWn in the art for achieving hydrodynamic cavitation including an exemplary system as provided by VRTX Technologies LLC of San Antonio, Tex., USA. Hydrodynamic cavitation equipment reduces the biomass particle siZe resulting in increased surface area of the cel lulose, hemicellulose, and lignin Within the solution. The [0087] Theterm“absorption”isWidelyacceptedinthe ultimateresultbeingincreasedsurfaceactivity,Whetherthe applicationofheatpumps forcooling.Absorption,inchem istry, is a physical or chemical phenomenon or a process in Which atoms, molecules, or ions enter some bulk phasei gas, liquid or solid material. This is a different process from adsorption, since the molecules are taken up by the volume, notby surface.Amore generalterm issorptionWhich covers adsorption,absorption,andionexchange. [0088] PretreatmentE?iciencyEnhancements [0089] TheutiliZationofabiomasssolutioncomprising the pretreatment step of solubiliZing biomass solution in ionic liquids is an optimal means of producing alternative energy fuels. Ionic liquids have the distinct advantage of being both superior ?uids for solubiliZing cellulose, hemi cellulose, and lignin from a variety of biomass sources. The preferred embodiment utiliZes liquid ionic phosphates “LlPs”, polyammonium ionic liquid sulfonamides “PILS”, poly(ionic liquids), or combinations thereof, With the addi tional distinct advantage of reduced premature solids (i.e., cellulose, etc.) precipitation When the biomass solution has a signi?cant (above 2%) moisture content. The ?uid, Which inthisinstanceisanionicliquidthatsolubiliZesthebiomass, is herein after referred to as the “solubiliZing ?uid”. [0090] Onespeci?callypreferredembodimentcombines the solubiliZing ?uid With at least one gas selected from the group consisting of carbon dioxide, ammonia, and methane. The bene?ts are particularly superior When the gas is pres suriZed to at least the supercritical pressure as a means of increasing mass transfer rates. [0091] TheintegrationofthesolubiliZing?uid,alsointer changeably referred to as the Working ?uid, for pretreatment of a biomass and as an absorbent Within an absorption heat pump/poWer generator has the further bene?t of increasing the energy balance associated With the production of biofu els such as ethanol or butanol. [0092] ReferringtoFIG.1,thepretreatmentprocessis depicted Where the biomass solution 10 is preferably extruded 20 to a pressure equivalent to the pressure of the supercritical carbon dioxide “ScCO2”30 that is absorbed into the solubiliZing ?uid phase of the biomass solution 10 as a supercritical liquid. The preferred source ofthe ScCO2 is desorbed from an integrated absorption heat pump. The utiliZationofanabsorptionheatpump greatlyreduces(on theorderofa90% reduction)theelectricityenergyrequire ments as compared to traditional compression of C02. The biomass solution infused With ScCO2 is further heated by a thermal generator 40, Which can be anything from process Waste heat of a poWer generating cycle, pyrolysis/gasi?ca tion Waste heat, to a traditional boiler, to the preferred hydrolysis temperature as knoWn in the art and speci?c to post treatment processes, as knoWn in the art, includes the catalytic or enZymatic breakdoWn ofthe cellulose, hemicel lulose,andligninsintofuelintermediaries.A ?ltrationand separation process step utiliZing the preferred micro- and/or nano-?ltration membranes 60 are utiliZed to isolate soluble components from in-soluble solid components, and subse quently undergo the traditional explosion process to further break the hydrogen bonding present in the cellulosic struc ture. The preferred embodiment extracts the available enthalpy from biomass solution via an energy extraction device 70, With the particularly preferred devices selected from the group consisting of gerotors, pressure exchanger, turbines, quasiturbines, pistons, and ramjet as a means of increasing the energy e?iciency of the fuel production process. The particularly preferred expansion devices are gerotors and ramjets, both having the advantage of high expansion e?iciency and loW damage susceptibility to pre cipitated cellulose and it’s byproducts. Yet further means of increasing the overall system e?iciency includes the selec tion of high e?iciency components for the expansion of ScCO2 stage including the utiliZation of high e?iciency gerotor, mechanical energy extraction device including gerotor, expansion turbine, expansion pump, Stirling cycle engine, Ericsson cycle engine, ramjet turbine, or combina tions thereof. The particularly preferred energy extraction devices are integral supersonic devices selected from the group consisting of gerotor, compressor and turbine includ ing compressors and turbines operating on either the ramjet orpulsejetprinciple. [0093] Also referring to FIG. 1, numerous means are knoWn in the art to increase the pressure of the biomass solution, though the preferred is an extruder 20 having the bene?ts of both reaching the desired pressure of the non compressible?uidWithhighenergye?iciency(compressing anon-compressible?uidrequiressigni?cantlyloWerenergy than a compressible ?uid, i.e.knoWn inthe artadvantages of any absorption heat pump vs. a vapor compression heat pump). The further infusion 30 of the supercritical carbon dioxide at the absorption pressure (Which is post the expan sion device/evaporator) into the biomass solution enables theScCO2 tobeabsorbedintotheionicliquid.A subsequent mechanicalmeans isusedtofurtherraisethepressureofthe biomass, ionic liquid, and carbon dioxide slurry to the generator/desorber pressure (i.e., high-pressure side of the thermodynamic cycle). The mechanical means include, though are not limited to, positive displacement pump, extruder, thermal hydraulic compressor/pump, or combina tions thereof. The utiliZation of the ionic liquid has the principaladvantageofconcurrentlyenablingtherapiddeg radationofthecellulose,hemicellulose,andligninproducts to byproducts capable, as knoWn in the art, of being cataPDF Image | United States Patent Application Publication US2007 0161095A1
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