EP2002010A2 - Synthèse de biocombustibles/biocarburants améliorant le rendement énergétique - Google Patents

Synthèse de biocombustibles/biocarburants améliorant le rendement énergétique

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Publication number
EP2002010A2
EP2002010A2 EP07754007A EP07754007A EP2002010A2 EP 2002010 A2 EP2002010 A2 EP 2002010A2 EP 07754007 A EP07754007 A EP 07754007A EP 07754007 A EP07754007 A EP 07754007A EP 2002010 A2 EP2002010 A2 EP 2002010A2
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Prior art keywords
biomass
biomass solution
solution according
working fluid
pressure
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EP07754007A
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German (de)
English (en)
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Llc Altervia Energy
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/59—Biological synthesis; Biological purification

Definitions

  • the invention is directed to the synthesis of biomass fuels utilizing supercritical fluids and ionic liquids and a range of supercritical process methods that enable high-energy efficiency conversion and transformation to alternative fuels including biofuels.
  • Ionic liquids "IL" can affect dissolution of celluloses from a variety of sources including plants, silk fibroin, and wool with no degradation of the solutes.
  • the solvation mechanism is proposed to involve the interaction of the IL chloride ions, which are non-hydrated and in a concentration of approximately 20 weight %.
  • the nonhydrated chloride ions present in solutions of this IL solvate carbohydrates by forming hydrogen bonds with their hydroxyl groups.
  • cellulose solutions in concentrations of up to 25 wt% can be obtained with [C4mim]Cl.
  • Ionic liquids including l-butyl-3-methyIimidazolium chloride
  • Ionic liquids as green solvents: 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, AL 35487
  • United States Patent No. 5,135,861 for "Method for producing ethanol from biomass” to Pavilon utilizes a mixture of biomass and water that subsequently produces carbon dioxide "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 CO2.
  • United States Patent Application No. 20020164731 for "Process for the simultaneous production of xylitol and ethanol” to Eroma, Olli-Pekka et al.
  • biomass hydrolysates selected from the group consisting of direct acid hydrolysis of said biomass, enzymatic prehydrolysate obtained by prehydrolysis of said biomass with steam or acetic acid, acid hydrolysis of prehydrolysate obtained by prehydrolysis of said biomass with steam or acetic acid, autohydrolysis using water or steam, and a sulphite pulping process.
  • United States Patent Application No. 20050069998 for "Procedure for the production of ethanol from lignocellulosic biomass using a new heat-tolerant yeast" to Ballesteros Perdices, Ignacio et al. utilizes traditional steam explosion pretreatment in with the combination of cellulase (CELLUCLAST 1.5L, from NOVO-NORDISK) and beta.glucosidase (NOVOZYME 188 from the NOVO-NORDISK) and culture of the heat- tolerant yeast Kluyveromyces marxianus CECT 10875.
  • CELLUCLAST 1.5L from NOVO-NORDISK
  • beta.glucosidase NOVOZYME 188 from the NOVO-NORDISK
  • United States Patent No. 6,090,595 for "Pretreatment process for conversion of cellulose to fuel ethanol" to Foody, et al. utilizes an improved pretreatment by varying the feedstock with a ratio of arabinoxylan to total nonstarch polysaccharides (AX/NSP) of greater than about 0.39, or a selectively bred feedstock on the basis of an increased ratio of AX/NSP over a starting feedstock material, and reacting at conditions that disrupt the fiber structure and hydrolyze a portion of the cellulose and hemicellulose.
  • AX/NSP arabinoxylan to total nonstarch polysaccharides
  • United States Patent Application No. 20040231661 for "Method of processing lignocellulosic feedstock for enhanced xylose and ethanol production" to Robert Griffin et al. utilizes multiple steps beginning with leaching a mechanically disrupted lignocellulosic feedstock prior to any pretreatment of the feedstock and ending with reacting said acidified feedstock under conditions which disrupt fiber structure and hydrolyse a portion of hemicellulose and cellulose of said acidified feedstock, to produce a composition comprising xylose and a pretreated feedstock.
  • Reacting acidified feedstock under conditions that disrupt the fiber structure are contemplated in the method of the '661 application and may be performed according to any method known in the art, for example, but not limited to pretreatment by steam explosion.
  • the '599 patent discloses a method for dissolving cellulose that comprises the steps of: (a) admixing cellulose with an ionic liquid comprised of cations and anions in the substantial absence of water to form an admixture, wherein said ionic liquid is molten at a temperature of about -44.degree. C. to about 12O.degree. C. wherein said cations contain a single five- membered ring that is free of fusion to other ring structures and said anions are halogen, pseudohalogen, or C.sub.l -C.sub.6 carboxylate; (b) irradiating said admixture with microwave radiation to assist in dissolution.
  • substantially absence and substantially free are used synonymously to mean that less than about 5 weight percent water is present, for example. More preferably, less than about one percent water is present in the composition.
  • the same meaning is intended regarding the presence of a nitrogen-containing base.
  • Cellulose can be dissolved without derivitization in high concentration in ionic liquids by heating to about lOO.degree. C, by heating to about 8O.degree. C. in an ultrasonic bath, and most effectively by using microwave heating of the samples using a domestic microwave oven. Using a microwave heater, it is preferred to heat the admixture of hydrophilic ionic liquid and cellulose to a temperature of about lOO.degree. to about 150.degree. C.
  • Microwave heating significantly enhances the dissolution of cellulose in ionic liquids.
  • Microwave-induced dissolution of cellulose in ionic liquids is a very quick process so that decay of the degree of polymerization is reduced. Being a relatively fast process, dissolution is energy efficient. Heating of the samples is usually required to enable dissolution. The effect of that heating may be to permit the ionic liquid solvent to penetrate into the fiber wall, which enables breaking of the fiber and microfibril structure and competitive hydrogen-bonding with encapsulated water.
  • Ionic liquids are very efficiently heated under microwave conditions. Thus, highly localized temperatures can be obtained that promote dissolution of cellulose by disrupting the strong, water mediated hydrogen-bonding of the natural polymer chains.
  • the products of fermentation are ethanol and carbon dioxide, produced in 1 :1 ratio as generally understood by those skilled in the art.
  • Biomass slurry is hydrolzyed in a fuel fired hydrolysis heater.
  • the organic acid in the waste is used as the hydrolysis catalyst.
  • carbon dioxide generated in a fermenter is fed to the hydrolysis heater as carbonic acid to provide the catalyst.
  • Such catalysts include dilute acid catalysts as selected from the group consisting of H.sub.2 SO.sub.4, HCl, HNO.sub.3, SO.sub.2 or any strong acid which effects pH values below about 3, and metal salt catalysts as selected from the group consisting of ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, aluminum chloride, and magnesium sulfate, Ni/Co, Rh/CeO.sub.2/M, where M represents SiO.sub.2, Al.sub.2O.sub.3 or ZrO.sub.2, Ni catalysts supported on zeolites (the use of zeolites as supports inhibited tar formation but promoted carbon deposition).
  • metal salt catalysts as selected from the group consisting of ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, aluminum chloride, and magnesium sulfate, Ni/Co, Rh/CeO.sub.2/M, where M represents SiO.
  • Discontinuous steam explosion treatment was patented in 1929 by Mason (U.S. Patent No. 1,655,618) for the production of boards of timber, and it combines a thermal treatment with steam and the mechanical disorganization of Iignocellulosic fibre.
  • the wooden splinters are treated with steam at a pressure of 3,5 MPa or higher, in a vertical steel cylinder. Once the treatment is completed, the material is violently discharged from the base of the cylinder. This process combines the effects on the Iignocellulosic material of high pressures and temperatures together with the final and sudden decompression.
  • Glucose can either serve as a feedstock for biochemical conversion (i.e., fermentation) to higher value products such as alcohol or organic acids, or it can be chemically converted (using catalytic processes) to products such as levulinic acid, sorbitol, and other polyols or glycols.
  • 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 five carbon sugars, the majority of which are xylose and arabinose.
  • Lignin is a complex polymeric heterogeneous material composed of variously substituted benzene rings.
  • Electricity is also a co-product of ethanol production generated at the rate of 2.28 kWh per gallon of ethanol or 68,692 MJ of electricity per hour.
  • the energy value for ethanol and the co-product electricity is about 6 x 1011 MJ/year.
  • the stover conversion process generates both ethanol and electricity and requires a small amount of non-renewable energy for feedstock production, transport, conversion, distribution and delivery to the end user. Because of the electricity generation, the conversion process actually produces a negative flow of non-renewable energy usage of -0.109 MJ per mile driven for ElOO as compared with 5.84 MJ nonrenewable energy per mile for gasoline.
  • enzymes must be stabilized, especially when utilized in supercritical fluids.
  • Exemplary enzymes include immobilized CALB (Novozyme), as noted in the paper titled “Single-Enzyme Nanoparticles Armored by a Nanometer-Scale Organic/Inorganic Network” by Jungbae Kim et al. of Pacific Northwest National Laboratory, 902 Battelle BlVd., P.O. Box 999, Richland, Washington 99352; where enzymes include cellulase (CELLUCLAST 1.5L, from the NOVO- NORDISK), and the .beta.-glucosidase enzyme is NOVOZYME 188 (NOVO-
  • Immobilization can further increase the enzyme stability including the utilization of carriers as selected from the group consisting of silicas, zeolites, aluminas and kaolins.
  • separation techniques include filtration recognized as microfiltration, ultrafiltration, and nanofiltration.
  • alternative fuels also include the production of methytetrahydrofuran from the Ievulinic acid, catalytic cellulignin fuel (United States Patent No. 6,855,180 for "Catalytic cellulignin fuel” to Pinatti, et al.) including furfural and Ievulinic acid from lignocellulose.
  • TiO2 prepared under calcination at 200°C exhibited high photocatalytic activity for degradation of NOx under both ultraviolet (UV) and visible-light illumination. It is also known in the art that titania-supported copper plays a crucial role for promoting the reduction of CO2.
  • Violuric acid (2,4,5,6(1 H,3H)-pyrimidine-tetrone 5-oxime, VOH) is often employed as an analytical reagent for chromatographic separation and for cation oxidation. It is also widely used in pulp bleaching techniques because the process is not very sensitive to temperature and pH variations. VOH can be also used as an efficient electron transfer mediator in oxidation processes allowing the increase of the global rate of electron transfer.
  • the mediator violuric acid forms a radical with a lifetime on the order of several tens of minutes which oxidizes the lignin.
  • the quality of the delignified pulp is remarkable due to the very high selectivity of the violuric acid radical in the oxidation of lignin over cellulose.
  • Another known method in the art is the methanol synthesis from carbon dioxide with a current efficiency of circa 90 by the electrolysis of carbon dioxide- saturated phosphate buffer solution in the presence of formate dehydrogenase and methanol dehydrogenase as electrocatalysts and pyrroloquinoline quinone as an electron relay.
  • a pretreatment process known in the art is depicted in the paper "Pretreatment for Cellulose Hydrolysis by Carbon Dioxide Explosion", by Yizhou Zheng et al. at the Laboratory of Renewable Resources Engineering, 1295 Potter Engineering Center, Purdue University, West Lafayette, Indiana 47906, Accepted September 21, 1998.
  • Zheng et al. uses an explosive release of the carbon dioxide pressure to disrupt the cellulosic structure as a means of increasing the accessible surface area of the cellulosic substrate to enzymatic hydrolysis. Results indicated that supercritical carbon dioxide is effective for pretreatment of cellulose.
  • An increase in pressure facilitates the faster penetration of carbon dioxide molecules into the crystalline structures, thus more glucose is produced from cellulosic materials after the explosion as compared to those without the pretreatment.
  • This explosion pretreatment enhances the rate of cellulosic material hydrolysis as well as increases glucose yield by as much as 50%.
  • the art lacks a high energy efficiency biomass fuel conversion solution with the additional inherent features of carbon dioxide sequestration by integrating a supercritical carbon dioxide hybrid absorption heat pump with integral power generating thermodynamic cycle.
  • a biomass to biofuel as a standalone plant and yet further integrated with a biomass to biodiesel plant process method having superior energy balance and higher value added co-products is provided.
  • the process preferably uses an integrated carbon dioxide absorption heat pump and power generation cycle that utilizes a liquid, non-toxic absorbent such as ionic liquids, from which the carbon dioxide gas is absorbed, that further enhances the biomass hydrolysis process.
  • a liquid, non-toxic absorbent such as ionic liquids
  • the present invention is an ionic liquid hybrid solution utilized within thermal energy transformation devices.
  • the devices use a solution comprised of ionic liquids that is an effective thermal transport media.
  • Additional combinations of refrigerants and absorbers are recognized in the art as having partial miscibility.
  • a further aspect of the invention is the achievement of phase separation as a function of at least one function selected from the group consisting of temperature, pressure, and pH.
  • the preferred solution further includes the utilization of small variations in pH to vary solubility of the refrigerant within the absorber.
  • the more preferred solution varies temperature and pressure, in combination with pH control, using methods including electrodialysis. Additional methods to enable phase separation include the application of electrostatic fields, as electrostatic fields increase solubility of ionic fluids.
  • One aspect of the invention is to integrate an absorption heat pump with integral power extraction capabilities to a standard biomass pretreatment process.
  • Fig. 1 is a process flow chart view depicting an exemplary series of steps from biomass pretreatment process to energy generation.
  • Fig. 2 is a process flow chart view depicting another exemplary series of steps from biomass pretreatment to microchannel injection of supercritical water through carbon dioxide sequestration.
  • Fig. 3 is a process flow chart view depicting an exemplary series of steps integrating both thermal means and photocatalytic exposure leveraging the additional solar alternative energy.
  • Fig. 4 is a A process flow chart view depicting an exemplary integration of supercritical carbon dioxide absorption heat pump system with supercritical pretreatment of biomass.
  • Fig. 5 is a A process flow chart view depicting another exemplary direct integration of binary solution of supercritical carbon dioxide and ionic liquids biomass pretreatment.
  • Fig. 6 is a A process flow chart view depicting the direct integration of a biomass to biofuel with a biomass to biodiesel.
  • Fig. 7 is a A process flow chart view depicting the direct integration of biomass to biofuel pretreatment step with an absorption heat pump having power generation capabilities.
  • Fig. 8 is an overview of the inputs and outputs of the biomass to biofuel conversion process.
  • Fig. 9 is a process flow chart view depicting an alternative distillation process for dehydration of biofuel by operating the distillation process as a binary solution Organic Rankine power generation thermodynamic cycle.
  • thermodynamic cycle is defined as a process in which a working fluid undergoes a series of state changes and finally returns to its initial state.
  • solar energy is defined as energy derived from the sun, which most often refers to the direct conversion of radiated photons into electrons or phonons through a wide range of means. Solar energy is also indirectly converted into additional energy forms such as the heating of ground water (a.k.a. geothermal water).
  • ionic liquids are defined as liquids that are highly solvating, non-coordinating medium in which a variety of organic and inorganic solutes are able to dissolve. They are effective solvents for a variety of compounds, and their lack of a measurable vapour pressure makes them a desirable substitute for Volatile Organic Compounds (VOCs). Ionic liquids are attractive solvents as they are nonvolatile, non-flammable, have a high thermal stability, and are relatively inexpensive to manufacture.
  • the key point about ionic liquids is that they are liquid salts, which means they consist of a salt that exists in the liquid phase and have to be manufactured; they are not simply salts dissolved in liquid. Usually one or both of the ions is particularly large and the cation has a low degree of symmetry. These factors result in ionic liquids having a reduced lattice energy and hence lower melting points.
  • thermal tolerant refers to the property of withstanding partial or complete inactivation by heat and can also be described as thermal resistance or thermal stability.
  • pressure train refers to independent pressure zones are alternatively produced by the utilization of flow control devices.
  • One such device is a pressure relief valve.
  • the utilization of a series of pressure relief valves, such that the cracking pressure is set incrementally to increase from the first pressure relief valve to the last with incremental increases for each pressure relief valve is an effective way to prevent backflow and to inherently control means to increase working fluid vapor state.
  • the aggregate of the series of pressure relief valves within a heat exchanger is hereinafter referred to as a "pressure train" heat exchanger.
  • pressure train heat exchanger.
  • Th e term "heat pumps” refers to a device for delivering heat or cooling to a system
  • a refrigerator is a device for removing heat from a system.
  • a refrigerator may be considered a type of heat pump.
  • TED thermal energy transformation device
  • an absorbent such as water, absorbs the refrigerant, typically ammonia, thus generating heat.
  • Ionic liquids and solids are recognized in the art of environmentally friendly solvents.
  • Ionic liquids "IL” have very low if not negligible vapor pressure and are preferably selected from the group consisting of ionic liquids compatible with supercritical carbon dioxide "scCO2".
  • the inventive combination of scCO2 and ILs have excellent carbon dioxide solubility and simple phase separation due to their classification as partially miscible fluid combinations.
  • Partially miscible fluids are both miscible and immiscible as a direct function of both pressure and temperature.
  • a partially miscible fluid in its immiscible state can be simply decanted for phase separation, which is inherently a low energy separation method.
  • the phase behavior of CO.sub.2 with ionic liquids and how the solubility of the gas in the liquid is influenced by the choice and structure of the cation and the anion.
  • heat pump is defined as the transport of thermal energy extracted from a heat source to a heat sink by means including vapor compression, absorption, and adsorption.
  • the term "electron acceptor” is a compound that receives or accepts an electron during cellular respiration. The process starts with the transfer of an electron from an electron donor. During this process (electron transport chain), the electron acceptor is reduced and the electron donor is oxidized. Examples of acceptors include oxygen, nitrate, iron (III), manganese (TV), sulfate, carbon dioxide, or in some cases the chlorinated solvents such as tetrachloroethene (PCE), trichloroethene (TCE), dichloroethene (DCE), and vinyl chloride (VC).
  • PCE tetrachloroethene
  • TCE trichloroethene
  • DCE dichloroethene
  • VC vinyl chloride
  • process intensification mixer is defined as the utilization of micromixing, particularly with supercritical fluids, to achieve high mass transfer.
  • Supercritical fluids include gases such as carbon dioxide, methane, methanol, ammonia, ethanol, butanol, and hydrogen.
  • the devices include hydrodynamic cavitation devices, spinning disk, and spinning tube in tube.
  • Absorption is widely accepted in the application of heat pumps for cooling.
  • Absorption in chemistry, is a physical or chemical phenomenon or a process in which atoms, molecules, or ions enter some bulk phase - gas, liquid or solid material. This is a different process from adsorption, since the molecules are taken up by the volume, not by surface.
  • a more general term is sorption which covers adsorption, absorption, and ion exchange.
  • Pretreatment Efficiency Enhancements The utilization of a biomass solution comprising 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 fluids for solubilizing cellulose, hemicellulose, and lignin from a variety of biomass sources.
  • the preferred embodiment utilizes liquid ionic phosphates "LIPs", polyammonium ionic liquid sulfonamides "PILS”, poly(ionic liquids), or combinations thereof, with the additional distinct advantage of reduced premature solids (i.e., cellulose, etc.) precipitation when the biomass solution has a significant (above 2%) moisture content.
  • the fluid which in this instance is an ionic liquid that solubilizes the biomass, is herein after referred to as the "solubilizing fluid".
  • the solubilizing fluid with at least one gas selected from the group consisting of carbon dioxide, ammonia, and methane. The benefits are particularly superior when the gas is pressurized to at least the supercritical pressure as a means of increasing mass transfer rates.
  • the integration of the solubilizing fluid, also interchangeably referred to as the working fluid, for pretreatment of a biomass and as an absorbent within an absorption heat pump / power generator has the further benefit of increasing the energy balance associated with the production of biofuels such as ethanol or butanol.
  • the pretreatment process is 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 fluid phase of the biomass solution 10 as a supercritical liquid.
  • the preferred source of the ScCO2 is desorbed from an integrated absorption heat pump. The utilization of an absorption heat pump greatly reduces (on the order of a 90% reduction) the electricity energy requirements as compared to traditional compression of CO2.
  • 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/gasification waste heat, to a traditional boiler, to the preferred hydrolysis temperature as known in the art and specific to the enzymatic and/or catalytic additives.
  • the resulting biomass solution is further processed utilizing the preferred process intensification mixer, including the depicted hydrodynamic cavitation device 50 that has an additional benefit of creating very high instantaneous pressures during the collapse of bubbles thus creating cavitation.
  • a wide range of equipment is known in the art for achieving hydrodynamic cavitation including an exemplary system as provided by VRTX Technologies LLC of San Antonio, Texas, USA.
  • Hydrodynamic cavitation equipment reduces the biomass particle size resulting in increased surface area of the cellulose, hemicellulose, and lignin within the solution.
  • the ultimate result being increased surface activity includes the catalytic or enzymatic breakdown of the cellulose, hemicellulose, and lignins into fuel intermediaries.
  • a filtration and separation process step utilizing the preferred micro- and/or nano-filtration membranes 60 are utilized to isolate soluble components from in-soluble solid components, and subsequently undergo the traditional explosion process to further break the hydrogen bonding present in the cellulosic structure.
  • 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 efficiency of the fuel production process.
  • the particularly preferred expansion devices are gerotors and ramjets, both having the advantage of high expansion efficiency and low damage susceptibility to precipitated cellulose and it's byproducts.
  • Yet further means of increasing the overall system efficiency includes the selection of high efficiency components for the expansion of ScCO2 stage including the utilization of high efficiency gerotor, mechanical energy extraction device including gerotor, expansion turbine, expansion pump, Stirling cycle engine, Ericsson cycle engine, ramjet turbine, or combinations thereof.
  • the particularly preferred energy extraction devices are integral supersonic devices selected from the group consisting of gerotor, compressor and turbine including compressors and turbines operating on either the ramjet or pulsejet principle.
  • a subsequent mechanical means is used to further raise the pressure of the 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 combinations thereof.
  • the utilization of the ionic liquid has the principal advantage of concurrently enabling the rapid degradation of the cellulose, hemicellulose, and lignin products to byproducts capable, as known in the art, of being catalytically or enzymatically converted to a wide range of combustible fuels, and the integral functionality of the high ScCO2 absorption enabling high efficiency power conversion.
  • the absorption power generation cycle can be either the primary energy generation cycle, a bottom cycle to other power generation thermodynamic cycles principally increasing the energy efficiency of the primary power generation cycle through energy recovery, a multi-effect absorption heat pump cycle, or incorporated into virtually any thermodynamic cycle driven by a thermal source.
  • the desorption "thermal generator" 40 stage is another net consumer of energy.
  • the energy consumption i.e., desorption temperature
  • the energy consumption can be decreased by means including the spinning disk reactor as a means of increasing the rate of heat transfer into/out of the biomass solution thus accelerating the absorption/desorption rate (thermally limited rates).
  • thermal-hydraulic compressor including a pressure train heat exchanger, a series of independent pressure stages having staggered or pulsed flow, hydraulic pump having an integral thermal sink, or combinations thereof.
  • the biomass solution is desorbed at higher efficiencies by utilizing the combination of at least one thermal method and at least one non-thermal method including non-thermal methods selected from the group consisting of magnetic refrigeration, vapor compression heat pump condenser, solar activated direct spectrum light absorption, electrodialysis, electrostatic fields, membrane separation, electrodesorption, pervaporation, gas centrifuge, vortex tube CO2-liquid absorber, decanting, or combinations thereof.
  • the utilization of fluids in combination with the biomass solution having regions ranging from miscibility, partial miscibility, or immiscibility enable high efficiency phase separation to be achieved by the varying operating parameters including at least one function selected from the group consisting of temperature, pressure, and pH.
  • Pretreatment of cellulose as a means to yield glucose is well established in the art, predominantly utilizing the energy intensive step of steam explosion.
  • the inventive utilization of processing the biomass into an ionic liquid enables a significant reduction in thermal energy and a lowering of the reaction temperature requirements.
  • the subsequent raising of the pressure of the biomass and ionic liquid slurry is achieved through mechanical means.
  • the resulting intermediate pressure biomass solution is preferably where the intermediate pressure is equivalent to the integral absorption cycle low-pressure stage (i.e., absorber pressure).
  • Another particularly preferred embodiment is further comprised of microwave irradiation to increase the hydrolysis rate by a minimum of 10%.
  • a specifically preferred embodiment immobilizes the enzymes within the working fluid by taking advantage of the ionic liquid's superior and specific absorption of microwave irradiation such that the enzymatic hydrolysis is enhanced by achieving a localized active catalytic center resulting in a reduction in the hydrolysis temperature of at least 5 degrees Fahrenheit lower than the pretreatment process void of microwave irradiation. The net result is reduced damage to proteins by thermal denaturing.
  • FIG. 3 is another embodiment of the pretreatment process where the particularly preferred reaction includes a photocatalytic process step 240 to further modify the biomass byproducts through the step of splitting hydrogen from the biomass solution, with a subsequent step of separating the hydrogen gas 250 by means known in the art.
  • a specifically preferred method of processing the supercritical biomass solution 10 is further comprised of process steps to heat the biomass solution by solar means.
  • a superior method is to utilize both supercritical solar flat panels 220 or supercritical solar concentrator receivers 230, whereby the optimal performance is achieved by configuring the solar devices in a sequential flow first into the supercritical solar flat panels and then into supercritical solar concentrator receivers as a means of minimizing capital cost and operating thermal losses.
  • the principal motivation for biomass to biofuel conversions is the reduction of global warming gases.
  • the creation of global warming gases is largely influenced and is a function of the energy balance associated with the production process.
  • the further inclusion and direct integration of an absorption heat pump having at least one working fluid component in fluid communication with the pretreatment process enables a reduction in energy consumption throughout the biomass conversion process and most notably in the energy intensive pretreatment process.
  • the further benefit of the integration of the absorption heat pump is the low energy production of supercritical gases, particularly CO2 as absorbed into a wide range of refrigerant absorbents including glycolic acid, alcohols, amyl acetate, isobutyl acetate, ILs, LIPs, and PILs.
  • the reduced energy requirement is attributed to the reduced electrical requirement of "compressing" a liquid as compared to compressing a gas.
  • the combined low energy process results in an increased biomass surface area to accelerate the hydrolyzing, oxidizing, and/or reducing reactions of the biomass solution.
  • the supercritical gas i.e., absorption heat pump refrigerant
  • the supercritical gas is optionally further integrated into the biomass conversion process as a means of reducing the moisture content that is naturally present in biomass to limit the premature precipitation of cellulose and hemicellulose from the pretreatment working fluid.
  • the supercritical gas most notably CO2 is then subsequently dehydrated into glycerine or glycerol (working fluid component Al, which is a byproduct of the biomass to biodiesel conversion process).
  • This dehydration process is significantly less energy intensive than traditional drying means of biomass, with the preferred moisture / water content of less than 2% on a weight basis of the working fluid.
  • the moisture saturated glycerine/glycerol is regenerated by at least in part utilizing the recovered waste heat from at least one working fluid A2 (which in this example is supercritical CO2) component in fluid communication with both the biomass to biofuel conversion process and biomass to biodiesel conversion processes.
  • FIG. 6 is an embodiment having true integration of a biomass to biofuel with a biomass to biodiesel conversion process.
  • the biofuel process is characterized as being comprised of a supercritical CO2 strong solution 600 that is desorbed, preferentially from an absorption heat pump, and dehydrated 601 by the infusion of the hydrated ScCO2 into the byproduct glycerine/glycerol from the biodiesel process.
  • the ScCO2 further contains lipids and extracts from biomass that are processed via an isolation / extraction process 619 as known in the art yielding high value add co- products 618 and lipids 625 utilized within the biodiesel process to be esterified 626 into biodiesel 627.
  • the hydrated glycerine/glycerol 620 can either be regenerated for reuse or is pyrolized/gasified 621 into either syngas or further catalytically processed 628 to additional value add co-products.
  • This pyrolysis/gasification stage 621 creates significant waste heat that can be recovered for multiple purposes via heat recovery system 629 including input thermal energy to the biomass to biofuel conversion process or the production of electricity 622, preferably via the aforementioned absorption heat pump/power generating cycle as thermal input into the generator/desorber.
  • the electricity produced 622 is optimally utilized for various electrochemical processes and/or creating microwave irradiation 623 as a means of increasing the rate of hydrolysis within the aforementioned hydrolysis process.
  • the isolation of the solubilizing fluid preferentially comprised of ionic liquid solution 604 having immobilized enzymes 605.
  • the pretreatment process of hydrolysis continues until such time as an aqueous solution 612, preferentially further comprised of electron transfer mediators, etc., is mixed via a process intensification mixer 606 creating a hydrated ionic liquid solution 607 yielding isolated extracts 613.
  • the water component of the hydrated solubilizing fluid creating "desorbed" high pressure steam 609 which in turn produces additional electricity 610 again producing waste heat 611 that is utilized within the aforementioned AFEX and/or absorption heat pump cycles.
  • the desorbtion of water from the solubilizing fluid is the desorbtion of ScCO2 that is transformed into co-products via either a catalytic reaction process 614 or is a feedstock to a subsequent fermentation/enzymatic process 614.
  • the fermentation/enzymatic process 614 yields additional CO2 which is absorbed into the solubilizing fluid (in the weak solution state) 615.
  • the now strong solution is electrochemically reduced 616 creating methane/methanol 617, wherein the electrochemical process is driven off the generated electricity 610.
  • FIG. 8 is the overall raw material inputs and resulting products and co-products by implementing the aforementioned integrated biofuel and biodiesel processes, which is referred to as the AlterVia process 710.
  • a cellulosic biomass 700 or agricultural products 705 are raw material inputs.
  • the first direct output is biodiesel 720 with its byproduct of glycerine 715 that is utilized as an input on the biofuel process side as characterized earlier.
  • the second direct output is a biofuel including ethanol or butanol 725 with its byproduct of CO2 730 that is further processed by electrochemical reduction into methanol 735 and becomes an input on the biodiesel process side as characterized earlier.
  • Additional co-products include isolated extracts such as vitamins and plant extracts 740, protein hydrolysates and amino acids/peptides 745, antioxidants and polyphenols 750.
  • the further byproducts of waste heat are transformed into electricity 755, preferably by the aforementioned absorption heat pump/power generator.
  • the cellulosic fibers processed by the earlier characterized pretreatment process and microchannel precipitation process results in cellulosic nanowhiskers that are further processed into nanocomposites 760.
  • Secondary Efficiency Gains The subsequent infusion of carbon dioxide, especially supercritical carbon dioxide "ScCO2", has the secondary benefit of enhancing the biomass hydrolysis process.
  • the preferred biomass solution is pressurized to a pressure in excess of 600 psia.
  • a particularly preferred biomass solution is pressurized in excess of the supercritical pressure of carbon dioxide of 1073 psia, such that the biomass solution is within the supercritical region.
  • the benefits of operating within the supercritical range has many significant benefits as known in the art including reduced surface tension, thus enabling the further utilization of microchannel heat exchangers, microchannel reactors, and the high reactivity of supercritical fluids for both catalytic and enzymatic chemical transformations.
  • a source of carbon dioxide, as a further means of reducing the carbon dioxide greenhouse effect is the integration of the fermentation byproduct of carbon dioxide being absorbed by the ionic liquid. It is further anticipated to incorporate the high efficiency biomass conversion system into alternative biomass to fuel conversion methods; additional power generation, industrial processes, waste treatment plants, or additional facilities that produce either waste heat or carbon dioxide. Therefore the inefficiencies and byproducts of one cycle are thus leveraged into the adjoining cycle providing real economic and greenhouse benefits beyond the operation of either single cycle system.
  • a particularly preferred absorption heat pump is further comprised of a power generation cycle to produce electricity utilized for at least one function selected from the group consisting of microwave irradiation, electrochemical reduction, and electrolysis.
  • the direct integration of the power generating cycle has the means to reduce the cost of electricity required to implement a series of critical process steps to enhance the biomass conversion process while also producing waste heat recovered from the bottom cycle, which becomes in fluid communication with the biomass pretreatment process.
  • the expanded gas increases the temperature differential within the thermodynamic cycle, thus enabling a higher Camot efficiency.
  • the energy recovery process is further comprised of a waste heat recovery device to recover thermal energy from the condenser of the power generating thermodynamic cycle whereby thermal energy is further increased by the heat of absorption by the subsequent mixing of the expanded gas into at least one absorbent prior to recombining with biomass solution.
  • the temperature lift achieved by the heat of absorption increases the "quality" of the working fluid such that the thermal energy is utilize, at least in part, as a preheating stage.
  • the waste heat is utilized for at least one function selected from the group consisting of preheating the inputs of the rapid expansion pretreatment process, thermal hydraulic pump, and inputs of an absorption heat pump as a means of increasing fluid pressure.
  • Yet another embodiment is the utilization of a waste heat recovery device to recover thermal energy from the condenser of the power generating thermodynamic cycle in fluid communication with the biomass solution and wherein the thermal energy is utilized as at least a partial thermal energy source within an endothermic reaction.
  • a waste heat recovery device to recover thermal energy from the condenser of the power generating thermodynamic cycle in fluid communication with the biomass solution and wherein the thermal energy is utilized as at least a partial thermal energy source within an endothermic reaction.
  • the power generating thermodynamic cycle is comprised of a working fluid having at least a first working fluid Wl and a second working fluid W2.
  • Exemplary combinations for binary fluids are selected from the group consisting of carbon dioxide, ammonia, methanol, ethanol, butanol, and water. Particularly preferred combinations are CO2 and NH4, CO2 and methanol, CO2 and ethanol, or CO2 and butanol.
  • thermodynamic cycles in which the benefits will be realized include cycles selected from the group consisting of Goswami, Uehara, Kalina, Rankine, Carnot, Joule-Brayton, Ericsson, and Stirling cycles.
  • the preferred cycles are combination cycles in which the biomass conversion system leverages both waste heat and synergistic utilization of ionic liquids from any single thermodynamic cycle into a hybrid high efficiency thermodynamic cycle.
  • a particularly preferred operating mode for the power generating thermodynamic cycle is selected from the group consisting of binary Organic Rankine, Goswami, Kalina, and Camot cycles. The result is maximum power generation, overall energy efficiency, and reduced CO2 emissions.
  • Biomass 300 enters the pretreatment process 310 after being infused with thermal energy from an external source both within the pretreatment stage 310 from heat source 555 and with the explosion column 520 from heat source 560.
  • the biomass solution is separated into two streams of pretreated slurry 525 and explosion working fluid 530 (which is predominantly ammonia in the AFEX process).
  • the explosion working fluid 530 is subsequent infused with water 540 and mixed 535, which triggers the creation of thermal energy from the heat of absorption.
  • AFEX process then sequentially goes through two condensers, with the first being a traditional cooling tower 545 and the second requiring active cooling condenser 575 (thus the evaporator of a chiller) so that the combined water and ammonia solutions returns to a liquid requiring less energy to pump 550 the liquid, rather than compress a gas.
  • a preferred embodiment integrates an absorption heat pump/power generating cycle as characterized by generator/desorber stage 380 with subsequent heat recovery 390 that preheats the strong solution entering the generator, the subsequent expansion of the desorbed working fluid (preferably ScCO2 or supercritical ammonia) with integral energy extraction device 70 producing a low temperature expanded gas (i.e., producing cooling) in the evaporator 510.
  • the particularly preferred embodiment integrates the AFEX and absorption heat pump having fluid communications at various points.
  • the first improvement is such that waste heat is recovered from condenser 545 that is utilized at least as part of the preheat 565 utilized prior to the heat source 360 (if even necessary dependent on desorption temperature).
  • the second improvement is such that the cooling produced by the absorption heat pump made available to AFEX via evaporator 510 displaces the otherwise requirement for mechanical active cooling equipment.
  • the third improvement is the direct integration of an energy extraction device 330 capable of handling the high solids content while concurrently extracting energy during the rapid expansion stage.
  • Another improvement is the utilization of a pressure exchanger 515 following the filtration/separation membrane 60 wherein the solids are further process by a post pretreatment process 570, such that pressure is recovered from the pretreatment process with the non-pretreated biomass 300 to complete the cycle.
  • Another significant use of electricity is the conversion of the biomass conversion process byproduct of CO2 from the fermentation (or even gasification/pyrolysis) steps.
  • the CO2 byproduct with H2O is electrochemically reduced into methanol, which is then subsequently utilized as an input in the preferentially integrated biodiesel esterification process. This reduction reaction is best achieved within ILs, PILs, and/or LIPs due to the significant electrical conductivity in combination with the high CO2 absorption.
  • a further means of increasing the electrical conductivity and decreasing the working fluid viscosity is by adding carbonate solvents including propylene carbonate "PC” and dimethyl carbonate "DMC".
  • the absorbed CO2 can be further processed by means including reactions of polymerizing carbon dioxide or carbonate synthesis as an energy effective means of sequestering CO2.
  • the high electrical (and thermal conductivity which enhances heat transfer) conductivity makes the biomass solution superior for a wide range of chemical reactions particularly those enhanced by electrochemical, electrolysis, electrocatalytic, or photocatalytic process steps.
  • the further inclusion of nanoscale conductors and semiconductors as a means of increasing quantum mean free path, quantum dots, copper, Fe2+ ions, iron-sulfur cluster, or electrides increase the reaction rates.
  • the biodigestion of organic materials can be further enhanced by electrochemical process steps.
  • Electron donor sources include tocopherols, antioxidants, aromatics, etc.
  • Additional means of enhancing the conversion process is achieved by inclusion of at least one working fluid additive selected from the group consisting of electron transfer mediator including iron salts, derivatives of iron salts, potassium salts, lactic acid salts, derivatives of potassium salts, derivatives of lactic acid salts, phytic acid, gallic acid, potassium ferricyanide, polyoxometalates, violuric acid, polycationic protein, thialoto-bridged complexes, thiolated complexes, metalloproteins, protein complexes having an iron-sulfur cluster, trehalose complexes, iron-sulfur cluster, sodium-ammonia, sulfiir-ammonia, a chitosan complex including chitosan lactate, chitosan alpha lipoic acid, and thiolated chitosan, nanoscale catalyst, electrocatalyst, photocatalyst, electron donor, electron acceptor, ultraviolet absorber, infrared absorber, quantum dot
  • Yet another embodiment is the integration of an energy extraction device within the rapid expansion step occurring within explosion steps (ammonia fiber explosion, steam explosion, supercritical explosion). The result is the concurrent production of electricity and cooling which terminates the hydrolysis process.
  • the preferred energy extraction device includes a gerotor, pressure exchanger, and quasiturbine. These devices have the distinct advantage of enabling the pressure expansion with minimal impact of the biomass solids. Additional means for reducing the particle size of precipitated cellulose, which also increases surface area, utilizes a microchannel device having channels less than 10 microns prior to the expansion stage.
  • a preferred embodiment utilizes a rapid expansion step that occurs in a series of independent pressure drop stages comprised of at least a first pressure drop stage and a second pressure drop stage.
  • a particularly preferred pre-expansion pressure is a pressure greater than the fluid's supercritical pressure.
  • the first pressure drop stage has a pressure below at least one working fluid's supercritical pressure.
  • the utilization of the at least two pressure drop stages enables the maximum energy generating capability (i.e., transform thermal energy enthalpy of biomass solution into electricity) while minimizing viscosity issues associated with complete pressure letdown of the post-pretreatment biomass solids.
  • the second pressure drop stage occurs within a pressure exchanger with high pressure fluid being the biomass solution from the exit of the pretreatment process and low pressure fluid being the biomass solution prior to the pretreatment process, as a means of further increasing the energy balance of the biomass conversion process.
  • Fig. 9 is another embodiment that further improves the energy balance by transforming the traditional distillation process for the biofuel process (specifically ethanol) into an energy producing step having higher efficiencies than traditional single cycle electricity power plants.
  • the non-dehydrated / non-anhydrous ethanol "EtOH" 780 is preferably pumped 550 to a pressure above the supercritical pressure of at least one of the components within the EtOH and H2O solution.
  • the solution 780 is preheated 390 from thermal energy recovered from the water vapor/liquid 540 isolated by means known in the art including nanofiltration 60 and subsequently heated by a second stage heat source 360.
  • the combined fluid is now operating in the mode of a binary solution Organic Rankine cycle having an anticipated operating efficiency near 30% while concurrently yielding pure EtOH 785 high pressure supercritical fluid that is expanded through an energy device 70 and further evaporated 510, preferably by the evaporator of the aforementioned absorption heat pump.
  • Yet another embodiment is the infusion of at least one working fluid additive selected from the group consisting of monomers, polymers solubilized in the at least one working fluid, microspheres, and nanoscale powders having particle size less than 100 nanometers.
  • the particularly preferred additives are further comprised of immobilized enzymes, immobilized catalysts, or combinations thereof.
  • Superior additive distribution is achieved by mixing the biomass solution with additives by at least one process intensification mixer including hydrodynamic cavitation devices, spinning disk, and spinning tube in tube.
  • the utilization of microspheres serves multiple purposes including immobilizing enzymes for easy reuse and recovery of enzymes, reducing agglomeration of biomass solids post-pretreatment, reducing nanocomposite density while increasing polymeric strength.
  • the resulting biomass solids, most notably cellulose, are further processed into polymers, copolymers, or block copolymers.
  • Carbon Dioxide Sequestration Another feature of the inventive biomass conversion system is the subsequent processing the desorbed carbon dioxide post expansion, as a means of sequestering the carbon dioxide byproduct including means of polymerizing carbon dioxide or carbonate synthesis. Utilizing the desorbed carbon dioxide, which remains a high-pressure heat transfer fluid, continues to have relatively low surface tension enabling chemical reactions to take place within a microreactor.
  • the ScCO2 which is the preferred heat transfer fluid is isolated from the biomass solution, for utilization within the thermodynamic cycle as a means of producing heating, cooling, power, or combinations thereof with the inventive integration of the biomass conversion process with a ScCO2 absorption heat pump system.
  • a preferred working fluid for the absorption thermodynamic cycle is an ionic liquid, though an integrated bottom cycling absorption / desorption cycle is efficiently performed utilizing binary fluids comprised of at least materials selected from the group consisting of organic liquids, alcohols, ammonia, water, carbon dioxide, lithium chloride / bromide or combinations thereof.
  • a particularly preferred binary fluids are supercritical fluids.
  • the maximum pressure of the supercritical biomass solution is significantly in excess of 600 psia.
  • the high side pressure is a minimum of 1400 psia when the binary composition is isobutyl acetate or amyl acetate.
  • the specifically preferred pressure is up to 5,000 psia for ionic liquids that have thermal stability up to 450 degrees Celsius.
  • a specifically preferred biomass solution 10 is comprised of at least fluids selected from the group consisting of ionic liquids, carbon dioxide, and water.
  • a preferred implementation mode is the mixing of the supercritical carbon dioxide, ionic liquid, and biomass with the supercritical water within a microchannel heat exchanger 130.
  • the utilization of the microchannel heat exchanger generally minimizes the particle size of the precipitated cellulose to less than about 10 microns. Reaction products are then optionally separated immediately following microchannel reactor by separation methods known in the art 60.
  • the desorbed ScCO2 is sequestered 160 and further processed in a preferred embodiment into a high value added co-product by being chemically transformed within a high throughput microchannel mixer/reactor (a.k.a. process intensification mixer / reactor) 170.
  • a.k.a. process intensification mixer / reactor Alternatively or immediately prior to the microchannel heat exchanger is the mixing of the supercritical carbon dioxide, ionic liquid, and biomass with the supercritical water by hydrodynamic cavitation, which also has the benefit of intimate mixing virtually instantaneously.
  • the further integration of the absorption cycle and the biomass solution pretreatment process enables the expansion of the biomass solution to not only achieve rapid cooling for the subsequent quenching of the hydrolysis reaction, but also the concurrent extraction of energy (which can be either mechanical or electrical through methods known in the art of power generation).
  • the solution is rapidly quenched by at least one process step selected from the group consisting of the sequential processing of hydrodynamic cavitation and expansion of the supercritical biomass solution, sequential expansion of the supercritical biomass solution to below water's supercritical pressure followed by the step of expansion of the supercritical biomass solution to below carbon dioxide's supercritical pressure.
  • An optional step of performing carbon dioxide sequestration can be achieved at various points throughout the biomass conversion system (one such sequestration point is following the expansion of the biomass solution to below the point at which a significant water vapor component exists, which is largely a function of the post-ScCO2 step as known in the art ranging from chemical reactions producing carbonate products to polymerization.
  • the introduction of the intermediary expansion stage enables the water to be isolated from the biomass solution as a further means of controlling the conversion rate of the biomass to fuel.
  • Separating components within the biomass solution is achieved by means including at least one method selected from the group consisting of nanofiltration, decanting of immiscible solution components, or combinations thereof.
  • Each expansion stage has the further inclusion of energy extraction devices to produce mechanical or electrical energyand/or preceded respectively by filtration means as known in the art.
  • FIG. 4 discloses the multiple areas where heat transfer fluids through heat exchangers are in fluid communication between a biomass fuel conversion pretreatment process and an absorption heat pump system.
  • the series of steps having heat transfer include: a) biomass is combined with ionic liquid into a biomass solution 300; b) Pretreatment step including raising the temperature and pressure of the solution by thermal means 310; c) Heat recovery 320 from the post pretreatment solution utilized as at least the first stage of providing thermal energy (heat source 360)for the absorption heat pump generator 380; d) Expansion through energy extraction device 330 of the pretreatment solution followed by filtration / separation of the byproducts 60, which can alternatively be prior to the expansion step; and e) Heat recovery 350 from the end product of the pretreatment biomass solution through a heat exchanger as a heat sink 420 which is utilized to preheat the biomass as a means of reducing thermal energy requirements, and additionally preheating biomass from thermal energy recovered from the absorption heat pump absorber 410 which also includes
  • Absorption heat pumps as known in the art, have a series of heat exchangers for heat recovery 390 as a means of increasing the cooling Coefficient of Performance, including pre-cooling of the desorbed gas with heat recovery to preheat the strong solution prior to reaching the generator 380.
  • FIG. 5 Another exemplary layout is shown in Fig. 5 that also discloses the multiple areas where heat transfer fluids through heat exchangers are in fluid communication between a biomass fuel conversion pretreatment process and an absorption heat pump system.
  • the series of steps having heat transfer include: a) Biomass is combined with ionic liquid into a biomass solution 300 after being preheated by heat removed from the absorber of the absorption heat thermodynamic cycle 410 via heat recovery heat exchanger (heat sink 420); b) Pretreatment step including first stage of further raising the temperature and pressure of the solution by thermal means 370 and other catalytic or enzymatic processing as a means of transforming the biomass to a series of byproducts as known in the art for ultimate conversion to fuel; c) Biomass solution temperature is further raised by thermal means 360 into the generator / desorber 380; d) biomass pretreatment byproducts are isolated 60 from the desorbed ScCO2 utilizing means known in the art; e) heat recovery 390 from the desorbed ScCO2, which serves as precool
  • An exemplary ionic liquid for the inventive biomass conversion system is the use of the same ionic liquid utilized in the study of fruit ripening by high- resolution CNMR spectroscopy: 'green' solvents meet green bananas" by Diego A. Fort, Richard P. Swatloski, Patrick Moyna, Robin D. Rogers, and Guillermo Moyna, received (in Columbia, MO, USA) 23rd October 2005, accepted 15th December 2005, and first published as an Advance Article on the web 19th January 2006 wherein banana pulps at any ripening stage were completely dissolved, which is in the IL l- «-butyl-3- methylimidazolium chloride ([C4mim]Cl.
  • ILs are capable of dissolving carbohydrates ranging from simple sugars to polysaccharides.
  • the nonhydrated chloride ions solvate carbohydrates by forming hydrogen bonds with their hydroxyl groups that in turn disrupt the complex intermolecular hydrogen bonding network present in many polysaccharides and promote their dissolution.
  • High Value Co-products Another embodiment is comprised of a means to alter the composition of the protein fraction within the biomass solution.
  • the protein fraction is preferentially hydrolyzed into branched chain amino acids and peptides.
  • a particularly preferred pretreatment process occurs at temperatures where the protein fraction of the biomass solution is subjected to minimal denaturing.
  • the utilization of enzymes to concurrently hydrolyze cellulose, hemicellulose, and lignincellulose with protein hydrolysis is a unique approach.
  • the processing of proteins to protein hydrolysates, free amino acids, or peptides when combined with electron transfer mediators serves the dual role of debittering the resulting protein hydrolysates, free amino acids, or peptides after serving the role of enhancing the rate of hydrolysis during the pretreatment process. This dual role has the further advantage of not requiring extraction of the electron transfer mediator, when such electron transfer mediator is a food grade ingredient.
  • the specifically preferred method of processing a biomass solution is further comprised of debittering additives having both the ability to reduce the bitter taste of the free amino acids and peptides, and increasing the rate of at least one reaction selected from the group consisting of cellulose hydrolysis, protein hydrolysis, lignincellulose hydrolysis, electrochemical reduction of biomass conversion byproducts including carbon dioxide, electrochemical biodigestion, and electrochemical oxidation of biomass solution.
  • Additional dual purpose additives (debittering and enhancing biomass conversion) additives include trehalose (provide thermal stability to enzymes and proteins), electron transfer mediators, electron donors including lactic acid, mineral ions selected from the group consisting of calcium, ferrous, cupric, manganous, and magnesium (enhancing electron transfer and impacting taste receptors).
  • the biomass source is a feedstock selected from the group consisting of distiller's dried grain with solubles, com, switchgrass, oat, and rice.
  • Yet another embodiment is the isolation of protein fractions by enabling membrane filtration systems to effectively operate at pressures greater than the membrane design pressure as a means of increasing isolation efficiency.
  • the membrane filtration system is further comprised of a detector/controller to maintain the pressure across a microfiltration or nanoflltration membrane as a means of isolating protein fractions including protein hydrolysates, amino acids, and peptides wherein the pressure across the microfiltration or nanoflltration membrane is a pressure differential, and wherein the pressure differential is less than maximum microfiltration or nanofiltration membrane operating pressure.

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Abstract

Procédé très efficace pour la synthèse de biocombustibles/biocarburants accroissant l'effet synergique des liquides ioniques à la fois sur les gains importants liés au prétraitement de la biomasse et l'utilisation combinée de ces liquides et du dioxyde de carbone dans des conditions supercritiques pour la production d'énergie. L'utilisation stratégique d'échangeurs thermiques, de préférence échangeurs thermiques et réacteurs à microcanal, augmente encore l'efficacité et la performance du système par une récupération thermique élargie et l'utilisation directe de la solution de biomasse comme fluide de travail d'un cycle thermodynamique.
EP07754007A 2006-03-25 2007-03-26 Synthèse de biocombustibles/biocarburants améliorant le rendement énergétique Withdrawn EP2002010A2 (fr)

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