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US 2007/0161095A1 Jul.12,2007 sodium hydroxide, Which improved the digestibility of straw, many pre-treatments have been developed for ligno cellulosicmaterials.Ofthepre-treatmentstested,hydrother mal processes appear to be among the most effective for improvingtheaccessibilityofthesematerials.An example of these hydrothermal processes is described in Shell Inter national Research’s Spanish patent ES87/6829, Which uses steam at a temperature of 200-250 degree C. in a hermeti cally sealed reactor to treat previously ground biomass. [0024] DiscontinuoussteamexplosiontreatmentWaspat ented in 1929 by Mason (US. Pat. No. 1,655,618) for the production of boards of timber, and it combines a thermal treatment With steam and the mechanical disorganization of lignocellulosic ?bre. In this process, the Wooden splinters aretreatedWithsteamatapressureof3.5MPa orhigher,in a vertical steel cylinder. Once the treatment is completed, the material is violently discharged from the base of the cylin der. This process combines the effects on the lignocellulosic material of high pressures and temperatures together With the ?nal and sudden decompression. In the discontinuous steam explosion process developed by IOTECH Corpora tion, knoWn as “?ash hydrolysis”, the Wood is ground to a smallparticlesizeandsubjecttotemperaturesandpressures close to 230 degree C. and 500 psi, and once these condi tions are reached, itis suddenly discharged from the reactor. [0025] Glucosecaneitherserveasafeedstockforbio chemical conversion (i.e., fermentation) to higher value products such as alcohol or organic acids, or it can be chemicallyconverted(usingcatalyticprocesses)toproducts suchaslevulinicacid,sorbitol,andotherpolyolsorglycols. [0026] Researchers already have developed improved catalysts that enable cost-effective conversion of sugars that are not recovered during food processing into important chemicals called polyols. About four million tons of polyols are sold each year in the U.S., ultimately used in products like antifreeze, polyester ?bers, cosmetics and plastics. Polyols can be produced from plant-based sugars much more energy-efficiently and cost effectively than from petro leum, Which is hoW they are produced currently. [0027] Allformsofbiomasshavethesamemajorcom ponentsicellulose, hemicellulose, and lignin. Cellulose is the largest fraction (40 to 50%), hemicellulose is next (20 to 30%) and lignin is usually 15 to 20% of biomass. The cellulose is composed of linear polymers of the six-carbon sugar glucose linked by 1,4 glycosidic bonds. Hemicellulose is a complex of primarily ?ve carbon sugars, the majority of Which are xylose and arabinose. Lignin is a complex poly meric heterogeneous material composed of variously sub stituted benzene rings. [0028] Electricityisalsoaco-productofethanolproduc tiongeneratedattherateof2.28kWh pergallonofethanol or 68,692 M] of electricity per hour. The energy value for ethanol and the co-product electricity is about 6><1011 MJ/year. [0029] Thestoverconversionprocessgeneratesbothetha nol and electricity and requires a small amount of non reneWable energy for feedstock production, transport, con version, distribution and delivery to the end user. Because of the electricity generation, the conversion process actually producesanegativeHow ofnon-reneWableenergyusageof —0.109M] permiledrivenforE100ascomparedWith5.84 M] non-reneWableenergypermileforgasoline. [0030] It is Widely knoWn in the art that acids aid the solubilization of cellulose including sulfuric acid. [0031] ItisalsoWidelyknoWnintheartthatenzymesmust bestabilized,especiallyWhenutilizedinsupercritical?uids. Exemplary enzymes include immobilized CALB (Novozyme), as noted in the paper titled “Single-Enzyme Nanoparticles Armored by a Nanometer-Scale Organic/In organic NetWork” by Jungbae Kim et al. of Paci?c North West National Laboratory, 902 Battelle Blvd., PO. Box 999, Richland, Wash. 99352; Where enzymes include cellulase (CELLUCLAST 1.5L, from the NOVO-NORDISK), and the .beta.-glucosidase enzyme is NOVOZYME 188 (NOVO-NORDISK). Immobilization can further increase theenzyme stabilityincludingtheutilizationofcarriersas selected from the group consisting of silicas, zeolites, alu minas and kaolins. [0032] ItisalsoWidelyknoWnintheartthatutilizationof hightemperatureresistantenzymes (e.g.,heat-tolerantyeast Kluyveromyces marxianus CECT 10875) enhance the throughput and economics of fuel synthesis. [0033] ItisalsoWidelyknoWnintheartthatseparation techniques include ?ltration recognized as micro?ltration, ultra?ltration, and nano?ltration. [0034] ItisalsoWidelyknoWnintheartthatalternative fuels also include the production of methyltetrahydrofuran from the levulinic acid, catalytic cellulignin fuel (US. Pat. No. 6,855,180 for “Catalytic cellulignin fuel” to Pinatti, et al.)includingfurfuralandlevulinicacidfromlignocellulose. [0035] ItisalsoknoWnintheartthat“Developmentofthe Batch-Type and FloW-Type Supercritical Fluid Biomass ConversionSystems”byD.Kusdiana,E.Minami,K.Ehara, and S. Saka of Kyoto University International Symposium On Post-Petrofuels in the 21st Century Prospects in the Future of Biomass Energy, Sep. 3-4, 2002, Montreal, Que bec, Canada, pp. 276-279 has proven that the cellulose Was hydrolyzed in the supercritical Water to glucose in an extremely short time. [0036] ItisalsoknoWnintheartthat“Productionof Liquid Alkanes by Aqueous-Phase Processing of Biomass Derived Carbohydrates” by George W. Huber, Juben N. Chheda, Christopher J. Barrett, and James A. Dumesic, of Department of Chemical and Biological Engineering, Uni versity of Wisconsin at Madison, Madison, Wis. 53706, USA hasproventhatliquidalkanesareoftheappropriate molecular Weight to be used as transportation fuel compo nents,andtheycontain90% oftheenergyofthecarbohy drate and H2 feeds. Thus, there has been much interest in processes that ef?ciently convert alkanes to alkenes. [0037] ItisalsoknoWnintheartthatphotoirradiationhas been used to activate several metal complexes. [0038] AdditionalreferencesincludethefolloWing: [0039] “Highcombustionactivityofmethaneinducedby reforming gas over Ni/Al203 catalysts” by Baitao Li, Rit suko Watanabe, Kenji Maruyama, Mohammad Nurunnabi, KimioKunimori,andKeiichiTomishige,publishedinAppl. Catal. A: General, 290, 36-45 (2005). [0040] “CatalyticperformanceandpropertiesofCeria basedcatalystsforcycliccarbonatesynthesisfromglycol andcarbondioxide”byKeiichiTomishige,HiroakiYasuda,PDF Image | United States Patent Application Publication US2007 0161095A1
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