BRPI0709137A2 - Biomass Fuel Synthesis Methods for Increased Energy Efficiency - Google Patents

Abstract

BIOMASS FUEL SYNTHESIS METHODS FOR ENHANCED ENERGY EFFICIENCY. The present invention relates to a high-efficiency method for synthesizing biomass fuels by leveraging the synergistic impact of ionic liquids on both the significant increases in biomass pretreatment and the use of the combination of ionic liquids and carbon dioxide under supercritical conditions for power generation. The strategic use of heat exchangers, preferably microchannel heat exchangers and microchannel reactors additionally increases the efficiency and performance of the system through extensive heat recovery and the direct use of the biomass solution as the working fluid of a thermodynamic cycle.

Description

Report of the Invention Patent for "BIOMASS FUEL SYNTHESIS METHODS FOR INCREASED ENERGY EFFICIENCY".

Field of the Invention

The present invention relates to the synthesis of biofuel fuels using supercritical fluids and ionic liquids and a series of supercritical methods that enable high energy efficiency conversion and transformation to alternative fuels including biofuels.

Background

Cellulose ethanol requires more advanced pretreatment methods because the carbon components of sugar - cellulose and hemi-cellulose - are much more difficult to economically hydrolyze into fermentable sugars. After cellulose and hemicellulose have been saccharified, the remainder of the ethanol production process is similar to decereal ethanol. Hydrolysis (saccharification) decomposes the hydrogen bonds in the hemicellulose and cellulose fractions in their sugar components: pentose and hexoses. These sugars can then be fermented in ethanol.

"IL" ionic liquids can affect the dissolution of celluloses from a variety of sources including plants, silk fibroin, and non-degrading solute wool. In the case of cellulose, the solvation mechanism is intended to involve the interaction of IL1 chloride ions which are unhydrated and are in a concentration of approximately 20% by weight.

High resolution 13C NMR studies of cellulose and cellulose oligomers dissolved in ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([C4my] CI) show that b- (1A4) -chain glucose oligomers are disordered in this medium and have a conformational behavior which is parallel to that observed in water, and therefore, reveal that the polymer is disordered in IL solution as well.

The chloride ions present in [C4min] CI solutions, which are unhydrated and at a concentration of approximately 20% by weight, effectively disrupt the extensive polysaccharide hydrogen bonding network interacting with their oxyhydryl clusters. promoting cellulose dissolution without degradation by glycosidic bonds. In order to better understand how [C4min] CI affects cellulose dissolution, the conformational behavior of polysaccharide in solvation by this IL needs to be investigated.

ILs are capable of dissolving carbohydrates ranging from simple sugars to polysaccharides. Some of the best results in this regard have been obtained with [C4min] CI. As recently shown, the unhydrated chloride ions present in solutions of these IL solvate carbohydrates forming hydrogen bonds with their clusters oxidize it. For example, cellulose solutions at concentrations up to 25% by weight may be obtained with [C4 me] CI.

Ionic liquids including 1-Butyl-3-methylimidazolium chloride ("Ionic Iiquids 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 Alabama1 Tuscaloosa, AL 35487); "Use of ionic Iiquids in the study offruit ripening by high-resolution CRMN spectroscopy: Diego A. Fort et al. received (in Columbia, MO, USA) October 23, 2005, first published as an Early Web Article on January 19, 2006 in which banana pulps at any ripening stage can be completely dissolved in liquid-based soluble systems. (IL) 1- n -butyl-3-methylimidazolium chloride ([C 4 -min] CI).

Jose Iborra of the University of Murcia in Spain and others additionally used a combination of supercritical ionic carbon dioxide to help an enzyme transform some organic molecules. Unfortunately, enzymes typically do not work well on carbon dioxide. Therefore the Iborra group designed a biphasic reactor in which these organic raw materials are dissolved in supercritical carbon dioxide and passed through a chamber containing an Ievedura enzyme dissolved in an ionic liquid.

There is a wide range of pre-treatment processes including the following:

United States Patent No. 6,267,309 to "Municipal Soil Waste Processing Facility and Commercial Ethanol Production Process" Chieffalo1 et al. Uses concentrated sulfuric acid as a means to soil cellulose within a pre-stage. -treatment.

United States Patent No. 5,135,861 to "Method for producing ethanol from biomass" for Pavilon utilizes a mixture of biomass and water which subsequently produces carbon dioxide "CO2" as a byproduct. The carbon dioxide byproduct of the product The initial fermentation process subsequently assists the conversion of biomass by catalytic hydrolysis Patent No. 5,135,861 further limits the operating pressure well below the supercritical CO2 pressure.

United States Patent Application No. 920020164731 for "Process for the simultaneous production of xylitol and ethanol" for Eroma, Olli-Pekka et al. Uses traditional pretreatment processes for biomass hydrolysates selected from the group consisting of direct acid hydrolysis of said biomass, enzymatic prehydrolysate obtained by prehydrolysis of said steam or acetic acid biomass, acid hydrolysis of prehydrolysate obtained by prehydrolysis of said steam or acetic acid biomass, self hydrolysis using water or steam, and a process of sulfite pulping.

United States Patent No. 5,711,817 to "Method forthe continuous conversion of cellulosic material to sugai" for Titmas uses gravity as a means to increase the flow pressure of cellulosic liquid material (a./ca semifluid biomass pulp) to increase thermodynamic efficiency.

United States Patent Application No. 920050069998 for "Procedure for the production of ethanol from Iignocellu-losic biomass using a new heat-tolerant yeasf for Ballesteros Perdices, Ignacio et al. Utilizes traditional vapor blast pretreatment in a cellulase combination" (CELLUCLAST 1.5L from NOVO-NORDISK) and be-ta.glucosidase (NOVOZYME 188 from NOVO-NORDISK) and culture of the thermo-tolerant yeast Kluyveromyces marxianus CECT 10875.

United States Patent No. 6,090,595 for "Pretreatment process for conversion of cellulose to fuel ethanot" for Foody1 et al. Utilizes improved pretreatment by varying the feedstock with a ratio of aabinoxylan to total non-starch polysaccharides (AX / NSP) more than about 0.39, or a selectively produced feedstock based on an increased ratio of AX / NSP to a starting feedstock material, and reacting under conditions that break the structure of the fibers and hydrolyze a portion of the cellulose and hemicellulose Pretreatment in any other way remains traditional where pretreatment is performed with a steam blast or extrusion device during the reaction stage.

United States Patent Application No. 920040231661 for "Method of Processing Iignocellulosic Feedstock Forenhanced Xylose and Ethanol Product" for Robert Griffin et al. Utilizes multiple steps starting with leaching of a mechanically disrupted lignocellulosic feedstock prior to any pre-treatment of the material. and terminating with reaction of said acidified feedstock under conditions which disrupt the fiber structure and hydrolyze a portion of hemicellulose and cellulose of said acidified feedstock to produce a composition comprising xylose and a pretreated feedstock. The reaction of acidified raw material under conditions that disrupt the fiber structure is contemplated in the method of application Nq20040231661 and may be carried out according to any method known in the art, for example, but not limited to vapor explosion pretreatment. .

United States Patent No. 6,824,599 to a Processing and Processing of Cellulose Using Liquid Ionic for Swatloski et al. uses a method for dissolving cellulose which comprises mixing cellulose with a molten ionic liquid which is melted at a temperature of about -10 ° C to about 100 degrees Celsius and in the substantial absence of water or a nitrogen-containing base to form a mixture. In addition, Patent No. 6,824,599 discloses a method for dissolving cellulose comprising the steps of: (a) mixing cellulose with an ionic liquid consisting of cations and anions in the substantial absence of water to form a mixture, wherein said ionic liquid is fused at a temperature of about -44 degrees C. to about 120 degrees C. wherein said cations contain a single five-membered ring that is free of fusion to other ring structures said anions are halogen, pseudohalogen, or C .sub.1 -C.sub.6carboxylate; (b) irradiating said mixture with para-auxiliary microwave radiation upon dissolution. The terms "substantial absence" and "substantially free" are used synonymously to indicate that less than about 5 percent by weight of water is present, for example. More preferably, less than about one percent water is present in the composition. The same meaning is intended for the presence of a nitrogen-containing base. Cellulose can be dissolved in high concentration derivation in ionic liquids by heating to about 100 degrees C., heating to about 80 degrees C. in an ultrasonic bath, and effective using microwave heating of samples using a domestic microwave oven . Using a microwave heater, it is preferable to heat the mixture of hydrophilic ionic liquid and cellulose to a temperature of about 100 degrees to about 150 degrees C. Microwave heating significantly strengthens the dissolution of cellulose in ionic liquids. Microwave-induced dissolution of cellulose in ionic liquids is a very rapid process so that the decay of the degree of polymerization is reduced. Being a relatively fast process, dissolution is energy efficient. Heating of samples is generally required to allow dissolution. The effect of this heating may be to allow solvent ionic liquid to penetrate the fiber wall, which allows fiber disruption and microfibril structure and competitive hydrogen bonding with encapsulated water. Ionic liquids are heated very effectively under microwave conditions. Thus, highly localized temperatures can be obtained which promote cellulose dissolution by disrupting the strong water-mediated hydrogen bonding of the natural polymeric chains. It was seen that cellulose was precipitated from the ionic liquid solution by the addition of water. When the water content of the ionic liquid was greater than about 1 weight percent (approximately 0.5mol H.sub.2 O fraction), the solvent properties were significantly impaired and it was seen that fibrous cellulose It was no longer soluble.

Ethanol production from the fermentation of cellulosic materials such as grains is well known. The process is not effective, but is capable of producing very large quantities at a fairly reasonable cost. The process has the added advantage of producing the product worldwide and shipping it to other markets as needed. There are two important features of the process: one is the need for heat. The fermentation process requires constant temperatures for the biological activity of enzymes and microorganisms to perform the conversion. The second feature is the production of carbon dioxide (CO.sub.2) from the fermentation itself, but also from the use of fossil fuels to heat the process. The capture of CO.sub.2, also referred to in the following parts as "CO2", is sporadic among producers, resulting in a significant overall contribution to the industry's greenhouse gas pool.

Fermentation products are ethanol and carbon dioxide, produced in a 1: 1 ratio as generally understood by those skilled in the art.

The semi-fluid biomass slurry is hydrolyzed in an ignited fuel explosion hydrolysis heater. When biomass is fruit residue, the organic acid in the residue is used as the catalyst for hydrolysis. When biomass does not contain organic acid, carbon dioxide produced in a fermenter is introduced into the hydrolysis heater as carbonic acid to provide the catalyst.

It is also widely known in the art that catalysts accelerate a wide range of chemical reactions. Said catalysts include dilute acid catalysts as selected from the group consisting of H.sub.2 SO.sub.4, HCI, HNO.sub.3, SO.sub.2 or any strong acid which produces pH values below about 3, and metal salt catalysts as selected from the group consisting of ferrous sulphate, ferric sulfate, ferric chloride, aluminum sulfate, a-luminium chloride, and magnesium sulfate, Ni / Co, Rh / Ce0 .sub.2 / M, where M represents SiO.sub.2, Al.sub.20.sub.3 or ZrO.sub.2, Ni catalysts on zeolite supports (the use of zeolites as supports inhibited tar formation but promoted carbon deposition).

Pretreatment - Since 1919, when Beckmann patented an alkaline pretreatment based on sodium hydroxide impregnation, which increased straw digestibility, many pretreatments for lignocellulosic materials have been developed. Of the pretreatments tested, hydrothermal processes appear to be among the most effective in improving the accessibility of these materials. An example of such hydrothermal processes is described in the Spanish Patent of Shell International Research ES87 / 6829, which uses steam at a temperature of 200 to 250 degrees Celsius in a hermetically sealed reactor to treat previously crushed biomass.

Discontinuous steam explosion treatment was patented in 1929 by Mason (United States Patent No. 1,655,618) for the production of wood panels, and combines a steam heat treatment and mechanical disorganization of lignocellulosic fiber. In this process, the wood chips are steam treated at a pressure of 3.5 MPa or greater in a vertical steel cylinder. Once the treatment is completed, the material is violently discharged from the cylinder base. This process combines the effects on lignocellulosic material of high pressures and temperatures along with sudden and final decompression. In the discontinuous vapor explosion process developed by IOTECH Corporation, known as "scintillation hydrolysis", the wood is shredded to a small particle size and subjected to temperatures and pressures close to 230 degrees Celsius and 3.5 MPa ( 500 psi), and once these conditions are met, it is suddenly discharged from the reactor.

Glucose may serve either as a feedstock for biochemical conversion (i.e. fermentation) to higher value products such as alcohol or organic acids, or it may be chemically converted (using catalytic processes) to products such as levulinic acid, sorbitol, and others. polyols or glycols.

Researchers have already developed improved catalysts that allow for cost-effective sugar conversion that is not recovered during food processing into important chemicals called polyols. About four million tons of polyols are sold each year in the United States, primarily used in products such as antifreeze, polyester fibers, cosmetics and plastics. Polyols can be produced from plant-based sugars much more energy-efficient and cost-effectively than from petroleum, which is as they are currently produced.

All forms of biomass have the same major components - cellulose, hemicellulose, and lignin. Cellulose is the largest fraction (40 to 50%), hemicellulose comes next (20 to 30%) and lignin is usually 15 to 20% of biomass. Cellulose is made up of linear six-carbon glucose sugar polymers chained by 1.4 glycosidic bonds. Hemicelu-lose is a complex of essentially five-carbon sugars, most 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 electricity co-product is about 6 χ 1011 MJ / year.

The wheat straw conversion process generates both ethanol and electricity and requires a small amount of nonrenewable energy for raw material production, transportation, conversion, distribution and deliberation for the end user. Due to electricity production, the conversion process actually produces a negative flow of non-renewable energy use of -0.109 MJ per mile directed to E100 compared to 5.84 MJ non-renewable energy per mile for gasoline.

It is widely known in the art that acids assist in the solubilization of cellulose including sulfuric acid.

It is also widely known in the art that enzymes should be stabilized, especially when used in supercritical fluids. Typical enzymes include immobilized CALB (Novozyme), as mentioned in the essay entitled uSingIe-Enzyme Nanoparticles Armo-red by a Nanometer-Scale Organic / Organic Network 'by Jungbae Kim etal. Pacific Northwest National Laboratory, 902 Battelle BIVd., P.O. Box999, Richland1 Washington 99352; where enzymes include cellulase (CELLU-CLAST 1.5L from NOVO-NORDISK), and the enzyme .beta.-glucosidase is NO-VOZYME 188 (NOVO-NORDISK). Mobilization may further enhance enzymatic stability including the use of carriers selected from the group consisting of silicas, zeolites, alumines and kaolins.

It is also widely known in the art that the use of high temperature resistant enzymes (e.g., Kluyveromyces marxianus CECT 10875 yeast thermo-tolerant) enhances the productivity and economy of fuel synthesis.

It is also widely known in the art that separation techniques include recognized filtration such as microfiltration, ultrafiltration, and nanofiltration.

It is also widely known in the art that alternative fuels also include the production of methytetrahydrofuran from levulinic acid, catalytic cellulignin fuel (United States Patent No. 6,855,180 for "Catalytic cellulignin fuel" for Pinatti, etal.) Including furfural and lignocellulose levulinic acid.

It is also well known in the art that the "Develop-ment of the Batch-Type and Flow-Type Supercritical Fluid Biomass Conversion System" by D. Kusdiana1 E. Minami, K. Ehara, and S. Saka of KyotoUniversity International Symposium On Post-Petrofuels in the 21st CenturyProspects in the Future of Biomass Energy, Sep. 3-4, 2002, Montreal, Que-bec, Canada, pp.276-279 proved that cellulose was hydrolyzed in glucose supercritical water at a time. Extremely short.

It is also well known in the art that "Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohy-c / rates" by George W. Huber, Juben N. Chheda, Christopher J. Barrett1 and James A. Dumesic1 of the Department of Chemical and Biological Engineering1University of Wisconsin at Madison1 Madison1 Wl 53706, USA has proven that liquid alkanes are of the appropriate molecular weight to be used as transport fuel components, and contain 90% of the energy of carbohydrate and H2 feeds. Therefore, there was much more interest in processes that effectively convert alkanes to alkenes.

It is also known in the art that photoradiation has been used to activate various metal complexes.

Additional references include the following:

"High combustion activity of methane induced by reforming gasover NI / AI203 catalysts" by Baitao Li, Ritsuko Watanabe, Kenji Maruyama, Mohammad Nurunnabi, Kimio Kunimori1 and Keiichi Tomishige1 published in Apppl. Catai. A: General, 290, 36-45 (2005).

"Catalytic performance and properties of Ceria based catalysts for cyclic carbonate synthesis from glycol and carbon dioxide" by KeiichiTomishige1 Hiroaki Yasuda, Yuichi Yoshida, Mohammad Nurunnabi, BaitaoLi1 and Kimio Kunimori1 published in Green Chem., 6, 206-214 (2004).

"Selective formation of ethylene carbonate from ethylene glycoland carbon dioxide over Ce02-Zr02 solid solution catalyst 'by Keiichi To-mishige, Hiroaki Yasuda1 Mohammad Nurunnabi, Baitao Li1 and Kimio Kunimo-ri, published in Stud. Surf. Sei. Catai., 153 , 165-168 (2004).

"Modeling of carbon-catalyzed gasification of organic feedstocks in supercritical water for energy conversion" at http://www.dieter-ulber.de/BacheIorThesis; Dartmouth College (1997).

Biomass gasification experiments in supercritical water produced a force cycle using wet biomass as a fuel, in which the process uses biomass (22 wt% in water) pumped to 25 MPa in a feed extruder and heated to 600 ° C in a gasifying pain. There it is almost completely gasified to a medium heating value gas (15 MJ / kg) after about 30 seconds of permanence. The catalyst applied may be different types of carbon or activated carbon. The efficiency of this combined biomass / combined cycle supercritical gasifier (BISG / CC) is estimated to be 42%.

'Direct synthesis of organic carbonates from the reaction of CO2 with methanol and ethanol over CO2 catalyst' by Yuichi Yoshida, YokoArai, Shigeru Kado, Kimio Kunimori, and Keiichi Tomishige, published in Catai.Today, forthcoming.

The use of carbon dioxide as a starting material for the synthesis of organic compounds has long been a goal for chemists. Hydrogenation of carbon dioxide to formic acid, meta-nol and other organic substances is particularly attractive but difficult to maintain. Effective production of formic acid in a supercritical mixture of carbon dioxide and hydrogen containing a catalytic ruthenium phosphine complex is known in the art.

It is also known in the art, as in United States Patent No. 6,875,456, proteins hydrolyzed by enzymatic hydrolysis from a variety of sources are widely used in the food industry, specifically as a means for providing flavorings. To paralyze as many amino acids as possible, the enzymatic pathway employs complex mixtures of various endo- and exoproteases.

United States Patent No. 6,509,180 and United States Patent Application No. 2003/0077771, for "Process for Producing Ethanof" for Verser, et al. Produces ethanol with an acetate, acetic acid or mixtures thereof as a product. of intermediate conversion followed by enzymatic hydrolysis of sugars and amino acids prior to fermentation Patent No. 6,509,180 discloses amino acid conversion, again only as a bacterial single protein-intermediate intermediate conversion product.

It is further known that microwave assisted enzymatic digestion is performed as represented in an assay entitled "Protein Preparation and Enzymatic Digestion in Proteomic" by Wei Sun et al. Another example is represented in another assay entitled "Microwave-Assisted Hydrothermal Degradation of Silk Protein to Amino" Acidé by Armando T. Quitain et al. at Research Institute for Solvothermal Technology, 2217-43 Hayashi Takamatsu, Kagawa 761-0301, Japan, and Department of Ecological Engineering, Toyohashi University of Technology, Tempaku, Toyohashi 441-8580, Japan.

It is also known in the art in the essay entitled "Effect of carbonate solvents on conductivity and viscosity behavior of ionic acid" by Boor Singh Lalia et al. Department of Applied Physics, GND University, Amritsar-143005, India, and Polymer Electrolyte Fuel Cell Research Department, Korea Institute of Energy Research, 305-343, Daeje-on, Korea, that the effect of the addition of carbonate solvents such as propylene carbonate (PC) and dimethyl carbonate (DMC) in an ionic liquid results in a reduction in ionic liquid viscosity along with an increase in conductivity by more than one order of magnitude.

It is also known in the art that ionic liquids having the presence of water precipitate cellulose from the solution. The presence of ionic noliquid water significantly reduces cellulose solubility, presumably through competitive hydrogen binding to cellulose microfibrils which inhibits solubilization. Cellulose may be precipitated from the IL solution by the addition of water, or other precipitating solutions including ethanole acetone. United States Patent No. 5,846,393 to "Electrochemically-aided biodigestion of organic materials" to Clarke et al. It should also be noted that the presence of water in the ionic liquid significantly reduces the solubility of cellulose. In this view, an essay entitled 'A new category of Iiquid salt-liquid ionic phosphates (LlPsJ' by Robert Engel et al. Notes that, unlike ionic liquids carrying tetrachloroaluminate anion tetrafluoroborate, LIPs are non-reactive to water. Simple phosphate anions are water soluble, unlike their corresponding hexafluorophosphate salts. It is also known in the art that a photokalitic process particularly in combination with photosensitizing ions including photosensitizing ions selected from the group obtained from TiO.sub.2, ZnO , zinc, or WO.sub.3 leads to enhanced oxidative reactions.It is further known in the art that titanium oxide absorbs UV having a wavelength of about 400 nm or less to thereby excite electrons thereof. resulting electrons and holes hit the surfaces of titanium oxide particles, the electrons s and holes are combined with oxygen or water, thus generating several radicals. The resulting radicals exert an oxidizing effect to thereby oxidize and decompose adsorbed substances on the surfaces of the particles. In addition, Ti02 prepared under calcination at 200 ° C exhibited high photocatalytic activity for NOx degradation under both ultraviolet (UV) and visible light illumination. It is also well known in the art to cover titania support to play a crucial role in promoting CO2 reduction.

Another case recognizing the potential for photocatalytic oxidation in an essay entitled "Aqueous Photocatalytic Oxidation of Lignin and Humic Aeids with Supported Ti02" by Elina Portjanskaja et al., Department of Chemical Engineering, Tallinn University of Technology, Ehitajate tee5, Tallinn 19086, Estonia, and Department of Chemical Technology, Lappeenranta University of Technology, PO Box 20, 53851 Lappeenranta, Finland, where the addition of Fe2 + ions up to 0.05 mM to an Iignin solution leads to a dramatic increase, about 25%, on photocatalytic efficiency.

It is also known as observed in bio-bleaching studies that the use of violuric acid is an effective mediator for Iacase-catalyzed deligification of kraft pulps. 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 also be used as an effective electron transfer mediator in oxidation processes allowing for increased overall electron transfer rate. In the electrochemical oxidation omitting violuric acid forms a radical with a life of the order of several tens of minutes which oxidizes lignin. The quality of the delignified pulp is remarkable due to the very high selectivity of the violuric acid radical in lignin oxidation on cellulose.

Another method known in the art is the synthesis of methanol from carbon dioxide with a current efficiency of about 90 by electrolysis of saturated phosphate buffer carbon dioxide solution in the presence of dehydrogenase and methanol dehydrogenase formate as electrocatalysts and pyrroloquinoline quinone as an electron relay.

A link on the Internet at http://pubs.acs.org/cen/science/83/8340sci1.html7print notes Science & Techology, October 3, 2005, Volume 83, Number 40, pp. 25-30. 36-39, ACS MeetingNews entitled 'Green Polymer Field Blossom' discloses a clean solvent supercritical carbon dioxide and a natural catalyst, that is, an enzyme, makes unusual block copolymers. The compounds consist of empoli (lactic acid), derived from cornstarch, grafted onto cellulosic nanowhisker fillers produced by acid cellulose hydrolysis.uOur approach uses reactive groups on the surface of the nanocellulosics toinitiate the polymerization reaction of lactide, "according to Dorgan's group showed that eco-compounds composed of poly (lactic acid) and microcrystalline cellulose fillers have higher glass transition temperatures.

A pre-treatment process known in the art is described in the "Pretreatment for Cellulose Hydrolysis by Carbon Dioxide Explosion-Ori" assay 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 carbon dioxide pressure to disrupt the cellulosic structure as a means to increase the accessible surface area of the cellulosic substrate for hydrolysis. The results indicated that supercritical carbon dioxide is effective for cellulose pretreatment. A rise in pressure facilitates faster penetration of carbon dioxide molecules into crystalline structures, so more glucose is produced from cellulosic materials after compared to aqueless without pretreatment.This explosion pretreatment increases the hydrolysis rate of as well as increases glycosepor production by as much as 50%.

United States Patent Application No. 20060211096 for "Enzyme catalysis in the presence of ionic liquids" for Kragl, Udo et al. discloses a method for converting substances in the presence of enzymes as a catalyst into a reaction medium comprising at least one ionic liquid, wherein the enzyme is selected from the group consisting of oxidoreductases, lipases, galactosidases, glycosidases, liases and enzymes in class EC 6. Conclusively demonstrated that the presence of ionic liquids increases production by over 55% when its lactose as a cheap donor.

All cited references, including patent and non-patent literature, are hereby incorporated by reference in their entirety.

The technique lacks a fuel conversion solution

of high energy efficiency biomass with the additional inherent characteristics of carbon dioxide sequestration by integrating a supercritical hybrid carbon dioxide absorption heat pump with integral power generator cyclothermodynamic.

summary

A biofuel biomass is provided as a standalone plant and yet further integrated with a biodiesel biomass plant process method having superior energy balance and added value co-products. The process preferably uses a carbon-integrated dioxide absorption heat pump and power generation cycle which utilizes a non-toxic liquid absorber such as ionic liquids, from which carbon dioxide gas is absorbed, which additionally strengthens the hydrolysis process of the biomass. The additional incorporation of enhanced protein hydrolysis with the added advantage of removing the bitterness of free peptides and amino acids provides added value co-products rather than the traditional animal by-product.

In one embodiment, the present invention is an ionic liquid hybrid solution used within thermal energy transforming devices. The devices use a solution consisting of tonic liquids which is an effective means of thermal transport.

Additional combinations of refrigerants and absorbers are known in the art to have partial miscibility. An additional aspect of the invention is to obtain phase separation as a function of at least a function selected from the group consisting of temperature, pressure, and pH. The preferred solution further includes the use of slight variations in pH to vary the solubility of the refrigerant within the absorber. The most 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 the solubility of ionic fluids.

One aspect of the invention is to integrate a heat-absorbing heat pump with full force extraction capabilities into a standard biomass pretreatment process.

The figures represented within the report provide exemplary configurations of the most important components of the biomass conversion system. A detailed description of the figures is provided in the following paragraphs. Brief Description of the Drawings

Figure 1 is a flowchart view of the process depicting a typical series of biomass pretreatment process steps for power generation.

Figure 2 is a flowchart view of the process depicting another typical series of biomass pretreatment steps for supercritical water microchannel injection through carbon dioxide sequestration.

Figure 3 is a flowchart view of the process depicting a typical series of steps integrating both thermal media and photocatalytic exposure leveraging additional solar alternative energy.

Figure 4 is a flow chart view of process A depicting a typical integration of supercritical carbon dioxide absorption heat pump system with supercritical biomass pretreatment.

Figure 5 is a flow chart view of process A depicting another typical direct integration of binary supercritical carbon dioxide solution and ionic liquid biomass pretreatment.

Figure 6 is a flowchart view of process A depicting the direct integration of a biofuel biomass with a biodiesel biomass.

Figure 7 is a flowchart view of process A depicting direct integration of biomass to the biofuel pretreatment step with an absorption heating pump having power generation capabilities.

Figure 8 is an overview of biomass inputs and outputs for biofuel conversion process.

Figure 9 is a flowchart view of the process depicting an alternative distillation process for biofuel dehydration operating the distillation process as a thermodynamic organic Rankine force generation cycle of binary solution.

Detailed Description of Preferred Modalities

The term "thermodynamic cycle" is defined as a process in which a working fluid undergoes a series of state changes and ultimately returns to its initial state.

The term "solar energy" is defined as energy derived from the sun, which most often refers to the direct conversion of irradiated 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 groundwater (a.k.a. geothermal water).

The term "tonic liquids" "ILs" is defined as liquids which are highly solvating non-coordinating means in which a variety of organic and inorganic solubles are capable of dissolving. They are effective solvents for a variety of compounds, and their lack of measurable vapor pressure makes them a desirable substitute for volatile organic compounds (VOCs). Ionic liquids are attractive solvents since they are nonvolatile, nonflammable, have high thermal stability, and are relatively inexpensive to manufacture. The key point about ionic liquids is that they are liquid salts, meaning that they consist of a salt that exists in the liquid phase and must be manufactured; They are not simply salts dissolved in liquid. Generally one or both ions are particularly large and the cation has a low degree of symmetry. These factors result in ionic liquids having reduced Iattice energy and therefore lower melting points.

The term "thermal tolerant" refers to the property of withstanding partial or complete heat inactivation and may also be described as thermal resistance or thermal stability.

The term "pressure train" refers to independent pressure zones that are alternatively produced by the use of flow control devices. A similar device is a pressure relief valve. The use of a series of pressure relief valves, such that the cracking pressure is adjusted in increments from the first pressure relief valve to the last with incremental increases for each pressure relief valve. It is an effective way to prevent return current and inherently control means for increasing the vapor state of the working fluid. The aggregate of the pressure relief valve series within a heat exchanger is in the following parts referred to as a "pressure train" heat exchanger. In this way the pressure relief valve effectively creates independent zones within the pressure train. There are numerous methods known in the art for accurate and / or relative pressure control.

The term "heat pumps" refers to a device for paralyzing heat or cooling to a system, while a cooler is a device for removing heat from a system. Thus, a cooler can be considered a type of heating pump. From the beginning to the end of the application, reference will be made to a thermal energy transformation device in the following parts referred to as "TED" with the understanding that the designation of refrigerator, air conditioner, compressor, water heater , trigeneration, and cogeneration can be replaced without changing device operation, specifically TEDs that use supercritical and transcritical fluids.

In absorption heat pumps, an absorber, such as water, absorbs the typically ammonia refrigerant, thereby generating heat. When the combined solution is pressurized and then heated, the refrigerant is expelled. When the refrigerant is pre-cooled and expanded to a low pressure, provides cooling. The low pressure refrigerant is then combined with the low pressure exhaust solution to complete the cycle.

Ionic liquids and solids are recognized in the environmentally friendly solvent technique. "IL" ionic liquids have very low if not negligible vapor pressure and are preferably selected from the group consisting of "scCO2" supercritical carbon dioxide compatible ionic liquids. The combination of scCO2 and ILs of the invention 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 function of both pressure and temperature. A partially miscible fluid in its immiscible state can be simply de-selected for phase separation, which is inherently a low energy separation method. The behavior of the CO.sub.2 phase with ionic liquids and how the solubility of gas in the liquid is influenced by the choice and structure of cation and anion.

The term "electride" is defined as alkalides except that the anion is assumed to be simply an electron which is located in a region of the crystal between the complexed cations.

The term "supercritical" is defined as the point at which fluid has been exploited above its critical temperatures and pressures.

The term "heat pump" is defined as the transport of thermal energy extracted from a thermal source to a heat sink enclosure including steam compression, absorption, and adsorption.

The term "electron acceptor" is a compound that receives or accepts an electron during cellular respiration. The process begins 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, ni- tract, iron (III), manganese (IV), sulfate, carbon dioxide, or in some cases chlorinated solvents such as tetrachlorethylene (PCE), trichlorethylene (TCE), dichloroethene (DCE), and vinyl chloride (VC).

The term "process enhancing mixer" is defined as the use 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. Devices include hydrodynamic cavitation devices, draw discs, and draw tube inside tube.

The term "absorption" is widely accepted in the application of good heating bases for cooling. Absorption, in chemistry, is a physical or chemical phenomenon or a process in which atoms, molecules, or ions penetrate some phase of mass - gaseous, liquid, or solid material. This is a different process of adsorption, since molecules are seized by volume, not by surface. A more general term is sorption which covers sorption, absorption, and tonic exchange.

The use of a biomass solution comprising the solubilization pretreatment step of biomass solution in ionic liquids is an optimal means for producing alternative energy fuels.

Ionic liquids have the distinct advantage that they are both superior fluids for solubilizing cellulose, hemicellulose, and lignin from a variety of biomass sources. The preferred embodiment utilizes "LIPs" liquid ion phosphates, "PILS" polyammonium ionic liquid sulfonamides, and po-li (liquid ionic), or combinations thereof, with the distinct advantage of reduced premature solids precipitation (i.e. cellulose, etc.) when the biomass solution has a significant moisture content (up to 2%). The fluid, which in this case is an ionic liquid that solubilizes the abiomass, is referred to in the following parts as the "solubilizing fluid".

A specifically preferred embodiment combines the fluid solubilizer with at least one gas selected from the group consisting of carbon dioxide, ammonia, and methane. The benefits are particularly greater when the gas is pressurized to at least supercritical pressure as a means to increase mass transfer rates.

The integration of solubilizing fluid, also interchangeably referred to as working fluid, for pretreatment of a biomass and as an absorbent within an absorption heat pump / power generator has the added benefit of increasing the energy balance associated with the production of biofuels such as ethanol or butanol.

Referring to Figure 1, the pretreatment process is represented where the biomass solution 10 is preferably extruded 20 to a pressure equivalent to the pressure of the "ScCO2" supercritical carbon dioxide 30 which is absorbed in the solubilizing fluid phase. of the biomass solution 10 as a supercritical liquid. The preferred source of ScCO2 is from an integrated absorption heat pump. Using an absorption heating pump greatly reduces (by the order of 90% reduction) electricity requirements compared to traditional CO2 compression. The ScCO2 infused biomass solution is further heated by a thermal generator 40, which can be anything from process exhaust heat from a power generator cycle, pyrolysis / gasification exhaust heat, to a traditional boiler, to the preferred hydrolysis temperature. as known in the art and specific for enzymatic and / or catalytic additives. The resulting biomass solution is further processed using the preferred process intensifying mixer, including the illustrated hydrodynamic cavitation device 50 which has the added benefit of creating very high instantaneous pressures during bubble collapse of this cavitation modocreating. A wide range of equipment is known in the art for hydrodynamic cavitation including an exemplary system as provided by VRTX Technologies LLC of San Antonio, Texas, USA. Hydrodynamic cavitation equipment reduces the particle size of the pulp resulting in increased cellulose surface area, hemicellu. -lose, and Iignin within the solution. The end result is increased surface activity if post-treatment processes, as known in the art, include catalytic or enzymatic decomposition of cellulose, hemicellulose, and lignins in fuel intermediates. A stepping off of the filtration and separation process using the preferred microprocessor and / or nanofiltration membranes 60 is used to isolate soluble components from insoluble solid components, and subsequently undergo a traditional blast process to subsequently rupture. hydrogen bond present in the cellulosic structure. The preferred embodiment extracts available enthalpy from the biomass solution via an energy extraction device 70, with particularly preferred devices selected from the group consisting of generator rotors, depression changer, turbines, quasi-turbines, pistons, and air reaction motor. as a means to increase the energy efficiency of the fuel production process. Particularly preferred expansion devices are generator rotors and forced air reaction motors, both having the advantage of high expansion efficiency and low susceptibility to damage to precipitated cellulose and its byproducts. Still additional means to increase overall system efficiency include high efficiency component selection for ScC02 stage expansion including the use of high efficiency generator rotor, mechanical energy extraction device including generator rotor, expansion turbine, expansion pump, Stirling moped, Ericsson moped, forced air reaction engine turbine, or combinations thereof. Particularly preferred energy extraction devices are supersonic integral devices selected from the group consisting of generator rotor, compressor and turbine including compressors and turbines operating or on the principle of forced air or pulse-reactor motor.

Also with reference to Figure 1, numerous means are known in the art for increasing the pressure of the biomass solution, although the preferred one is an extruder 20 having the benefits of both achieving the desired pressure of the non-compressible fluid with high energy efficiency. energy (compressing a non-compressible fluid requires significantly less energy than a compressible fluid, that is, advantages known in the art of any absorption heating pump vs. a steam compression heating pump). Additional infusion of supercritical decarbon dioxide at the absorption pressure (which is after the expansion / evaporator device) in the biomass solution allows ScCO2 to be absorbed into the ionic liquid. A subsequent mechanical means is used to further increase the pressure of the semi-fluid slurry of biomass, ionic liquid, and carbon dioxide for generator / desorbent pressure (ie, high pressure side of the thermodynamic cycle). Mechanical means include, but are not limited to, positive displacement pump, extruder, compressor / hydraulic heating pump, or combinations thereof. The use of ionic liquid has the main advantage of simultaneously enabling rapid degradation of the products of cellulose, hemicellulose, elignin to by-products capable, as is well known in the art, of catalytically or enzymatically converted to a wide range of combustible fuels, and the full functionality of the high absorption of ScCO2 enabling high efficiency of force conversion. The absorption force generation cycle may be either the primary power generation cycle, a background cycle for other thermodynamic power generation cycles, principally increasing the energy efficiency of the primary power generation cycle through recovery of energy. energy, a multi-effect absorption heat pump cycle, or incorporated into virtually any thermodynamic cycle driven by a thermal source.

The desorption "thermal generator" stage 40 is another pure energy consumer. Energy consumption (i.e. desorption temperature) may be reduced by means including the jerking disc reactor as a means to increase the heat transfer rate to / from the biomass solution thereby accelerating the absorption / desorption rate (thermally limited rates). Additional means for increasing high lateral pressure include the use of a hydraulic heat pump including a pressure train heat exchanger, a series of independent pressure stages having alternating or pulsed flow, a hydraulic pump having an integral heat sink, or combinations thereof. same. The biomass solution is desorbed to greater efficiencies using a 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 cooling, steam compression pump condenser, direct spectrum light absorption. solaractivation, electrodialysis, electrostatic fields, membrane separation, electrodesorption, pervaporation, gas centrifuge, CO2-liquid absorber, vortex tube decantation, or combinations thereof. The use of fluids in combination with the biomass solution having regions ranging from miscibility, partial miscibility, or immiscibility allows high efficiency phase separation to be achieved by varying operating parameters including at least one function selected from the group consisting of temperature, pressure, and temperature. pH.

Cellulose pretreatment as a means for producing glucose is well established in the art, predominantly utilizing the intensive vapor burst energy step. The use of the invention to process biomass in an ionic liquid enables a significant reduction in thermal energy and a reduction in reaction temperature requirements. Subsequent increase in the pressure of the semifluid ionic biomass slurry is obtained by mechanical means. The resulting intermediate pressure biomass solution is preferably where the intermediate pressure is equivalent to the low pressure stage of the integral absorption cycle (ie absorber pressure).

Another particularly preferred embodiment is additionally microwave irradiation to increase the hydrolysis rate by a minimum of 10%. A specifically preferred embodiment immobilizes enzymes within the working fluid by taking advantage of the superior specific absorption of the microwave irradiation ionic liquid such that the enzymatic foot-reinforced foot reaching a catalyzed active catalytic center resulting in a reduction in the hydrolysis temperature of at least 5 Fahrenheit degrees less than the vacuum of the microwave radiation pretreatment process. The net result is reduced damage to proteins by thermal denaturation.

When the pretreatment biomass conversion process is either enzymatic or requires a temperature increase beyond the temperature at which proteins denature or enzymes lose their activity, the additional inclusion of trehalose enhances effective enzyme life and limits protein denaturation. Numerous distinct advantages are present when the conversion of biomass to fuel is preferably achieved using catalytic reactions, with the preferred catalysts selected from the group consisting of submicron catalysts, submicron electrocatalysts, or submicron photocatalysts where submicron and in the field. -scale are used interchangeably. It is known in the catalytic reaction technique that high nanoscale area surface (i.e. submicron crystallite department size) and either photon or electron activation accelerates the reaction chemistry leading to both higher energy efficiency and reduced damping costs. capital. The distinct combined advantages realized by the preferred solubilizing fluid, the integration of the low energy requirement absorption heat pump to obtain supercritical pressures, the integration of energy extraction to transform mental copy into a useful co-product of electricity, and transfer high mass of supercritical reactions produces superior biomass conversion over a wide range of nanocomponent polymer products to biofuels.

Referring to Figure 3 is another embodiment of the pre-treatment process where the particularly preferred reaction includes a stepped photocatalytic process 240 for additionally modifying biomass by-products by the step of dividing hydrogen from the biomass solution, with a subsequent step of separating the hydrogen gas. 250 by means of knowledge in the art. A specifically preferred method of processing supercritical biomass solution 10 is furthermore in process steps for heating the biomass solution by solar means. A superior method is to use either supercritical solar flat panels220 or supercritical solar concentrator receivers 230, whereby optimum performance is achieved by setting the solar devices to a sequential flow first on supercritical solar flat panels and then supercritical solar concentrator receivers as a means to minimize the cost of capital and operate thermal losses.

The main motivation for biomass to biofuel conversions, in other words the production of alternative energy fuels, is the reduction of global warming gases. The creation of global warming gases is largely influenced and is a consequence of the energy balance associated with the production process. Therefore, the additional inclusion and direct integration of an absorption heating pump having at least one working fluid component in fluid communication with the pretreatment process enables a reduction in energy consumption from start to finish. end of the biomass conversion process and most notably in the energy intensive pretreatment process. An additional benefit of the absorption heat pump integration is the low energy production of supercritical gases, particularly as absorbed in a wide range of refrigerant absorbers including glycolic acid, alcohols, amyl acetate, isobutyl acetate, ILs, LIPs, and PILs. The need for reduced energy is attributed to the need for reduced electricity to "compress" a liquid compared to compressing a gas.

The combined low energy process results in an increase in biomass surface area by accelerating hydrolysis, oxidation, and / or biomass solution reduction reactions. Supercritical gas (ie absorption refrigeration pump cooler) is optionally further integrated into the biomass conversion process as a means to reduce the moisture content that is naturally present in the biomass to limit premature precipitation. cellulose and hemicellulose fluid from the pre-treatment work. The supercritical gas, most notably CO2, is subsequently subsequently dehydrated to glycerine or glycerol (as a working fluid component A1, which is a biomass by-product for the biodiesel conversion process). This dehydration process is significantly less energy intensive than traditional biomass drying medium, with the preferred moisture / water content of less than 2% on a weight basis of the working fluid. The moisture-saturated glycerin / glycerol is regenerated at least in part using recovered heat from at least one working fluid component A2 (which in this example is supercritical CO2) in fluid communication as well. biomass for biofuel conversion process and biomass for biodiesel conversion processes.

Referring to Figure 6 it is one embodiment having true integration of a biomass for biofuel with a biomass for biodiesel conversion process. The biofuel process is characterized as consisting of a strong supercritical CO2 solution 600 which is desorbed, preferably from a heat-absorbing heat pump, and dehydrated 601 by infusion of hydrated ScCO2 into the glycerine / glycerol byproduct of the biodiesel process. This transforms the high moisture content biomass 602 into a low moisture biomass solution 603 having increased compatibility with the solubilizing fluid. ScC02 additionally contains lipids and biomass extracts which are processed through an isolation / extraction process 619 as known in the art to produce high value added co-products 618 and lipids 625 used within the biodiesel process to be esterified. 626 in biodiesel 627. Hydrated glycerine / glycerol 620 may be either regenerated for reuse or is pyrolyzed / gasified 621 in or singas or further catalytically processed 628 for additional value added co-products. This 621 pyrolysis / gasification stage creates significant exhaust heat that can be recovered for multiple purposes through the 629 heat recovery system including thermal energy input to the biomass for biofuel conversion process or electricity generation 622, preferably via the aforementioned absorption heat pump / power generator cycle as thermal input to the generator / desorbent. This produced electricity 622 is optimally used for various electrochemical processes and / or for creating microwave irradiation 623 as a means to increase the hydrolysis rate within the above hydrolysis process. In addition to the biofuel conversion process is the isolation of the lubricating fluid, preferably consisting of ionic fluid solution 604 having immobilized enzymes 605. The hydrolysis pretreatment process continues to date as an aqueous solution 612, preferably additionally consisting of electron transfer mediators, etc., is mixed through a process intensifying mixer 606 creating a solution of hydrated ionic liquid 607 producing isolated extracts 613. The water component of the hydrating solubilizing fluid creating high vapor "desorbed" pressure 609 which in turn produces additional electricity 610 again producing exhaust heat 611 which is used within the aforementioned AFEX and / or absorption heat pump cycles. Additionally, as a result of the desubtion of water solubilizing fluid is the desorption of ScCO2 which is co-produced by either a catalytic reaction process 614 or is a raw material for a subsequent fermentation / enzymatic process 614. fermentation / enzymatic process 614 produces additional CO2 which is absorbed into the solubilizing fluid (in the weak solution state) 615. The strong new solution is reduced electrochemically 616 creating methane / methanol617, where the electrochemical process is rejecting the generated electricity 610.

Referring to Figure 8 are the global inputs of raw materials and resulting products and co-products implementing the aforementioned integrated bio-fuel and biodiesel processes, which is referred to as the AIterVia 710 process. A cellulosic biomass 700 or agricultural products705 (most notably products with a significant protein content) are raw material inputs. The first direct output is 720 biodiesel with its glycerine by-product 715 which is used as an input in the side biofuel process as previously characterized. The second direct output is a biofuel including ethanol or butanol725 with its by-product of CO 2 730 which It is further processed by electrochemical reduction in methanol 735 and becomes an input to the lateral biodiesel process as previously characterized. Additional by-products include isolated extracts such as vitamins and plant extracts 740, protein hydrolysates and amino acids / peptides 745, antioxidants and polyphenols 750. Additional exhaust heat by-products are transformed into electricity 755, preferably by the aforementioned pumps. heater / power generator. And lastly, the cellulosic fibers processed by the previously characterized pretreatment process and microchannel precipitation process results in cellulosic nanowhiskers which are further processed into 760 nanocomposites.

Secondary Efficiency Gains - Subsequent infusion of carbon dioxide, especially "ScC02" supercritical carbon dioxide, has the secondary benefit of enhancing the biomass hydrolysis process. The preferred biomass solution is pressurized to an excess pressure of 12.9 MPa gauge (600 psia). A particularly preferred biomass solution is pressurized in excess of the supercritical carbon dioxide pressure of 23 MPa (1073 psia) such that the biomass solution is within the supercritical region. The benefits of operating within the supercritical range have very significant benefits as is well known in the art including reduced surface tension, thereby enabling the subsequent use of microchannel heat exchangers, microchannel reactors, and the high reactivity of supercritical flows for both catalytic and enzymatic chemical transformations. One source of carbon dioxide, as an additional means to reduce the greenhouse effect of carbon dioxide, is the integration of the carbon dioxide fermentation byproduct being absorbed by the ionic liquid. It is further envisaged to incorporate the high efficiency biomass conversion system into methods of converting biomass to alternative fuels; additional power generation, industrial processes, waste disposal plants, or additional facilities that produce either exhaust heat or carbon dioxide. Therefore the inefficiencies and byproducts of one cycle are therefore leveraged in the adjacent cycle providing real economic and greenhouse benefits beyond the operation of any single cycle system.

A particularly preferred absorption heat pump further consists of a power generation cycle to produce electricity used for at least one function selected from the group consisting of microwave irradiation, electrochemical reduction, and electrolyte. Direct integration of the power generator cycle has the means to reduce the electricity cost required to implement a series of critical process steps to reinforce the biomass conversion process at the same time as also producing exhaust heat recovered from the bottom cyclode. which becomes fluid communication with the biomass pre-treatment process.

Another benefit of integrating the rapid expansion pretreatment process having an expanded gas and a force-generating thermodynamic cycle, wherein the expanded gas of the pretreatment process is in fluid communication with the force-generating thermodynamic cycle condenser, is to increase the efficiency of the thermodynamic cycle of both the biomass pretreatment process and the force generator thermodynamic cycle. Expanded gas increases the differential temperature within the cyclothermodynamic, thus allowing for greater Carnot efficiency. The energy recovery process further consists of an exhaust heat recovery device for recovering thermal energy from the thermodynamic power generating cycle condenser whereby the thermal energy is further increased by the heat of absorption by the subsequent mixing of the expanded gas in at least one absorbent to recombine with the biomass solution. Increasing the temperature obtained by the heat of absorption increases the "quality" of the working fluid such that thermal energy is used at least in part as a preheat stage. Exhaust heat is used for at least one function selected from the group consisting of preheating rapid expansion pre-treatment process inlets, hydraulic heating pump, and absorption heat pump inlets as a means for increase fluid pressure.

Still another embodiment is the use of an exhaust heat recovery device to recover thermal energy from the thermodynamic cycle power generator condenser in fluid communication with the biomass solution and wherein the thermal energy It is used with at least a partial thermal energy source within an endo-thermal reaction. Using low "quality" exhaust heat as a first preheat stage in an endothermic reaction (such as glucose pyrolysis) increases the energy efficiency of the combined cycle.

Another embodiment leverages the advantages of binary fluids simultaneously within the biomass and power cyclogenerator pretreatment process. Binary fluids Achieve superior energy efficiency within Organic Rankine cycles, while the same binary fluids increase the hydrolysis rate within the biomass pretreatment process. Therefore the force-generating thermodynamic cycle consists of a working fluid having at least a first working fluid W1 and a second working fluid W2. Typical 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. Preferred cyclosterodynamics in which the benefits will be realized include selected cycles among the group consisting of Goswami, Uehara, Kalina, Rankine, Carnot, Joule-Brayton, Ericsson, and Stirling cycles. Preferred cyclos are combination cycles in which the biomass conversion system leverages both exhaust heat and synergistic use of ionic liquids of any single thermodynamic cycle in a high efficiency hybrid cyclothermodynamic. A particularly preferred operating mode for the force-generating thermodynamic cycle is selected from the group consisting of binary cycles Organic Rankine, Goswami, Kalina, and Carnot. The result is maximum power generation, overall energy efficiency, and reduced CO2 emissions.

Referring to Figure 7, it is another embodiment that represents a significant reduction in power requirements beyond the improved "A-FEX" process of ammonia fiber explosion. The enhanced AFEX process is characterized as follows: Biomass 300 enters the pretreatment process 310 after being infused with thermal energy from an external source both within the pretreatment stage 310 of the 555 heat source and with blast column 520 of heat source 560. The biomass solution is separated into two streams of pretreated semifluid pulp 525 and blast working fluid 530 (which is predominantly ammonia in the AFEX process). Explosion working fluid 530 is then infused with water 540 and mixed 535, which triggers the generation of thermal energy from absorption heat. The AFEX process is then sequentially passed through two capacitors, with the first being a traditional 545 cooling dam and the second requiring active cooling dam 575 (hence a chiller evaporator) so that the combined water and ammonia solutions return to a liquid requiring less energy. to pump 550 liquid rather than compressing a gas. A preferred embodiment comprises an absorption heat pump / power generator cycle as characterized by the generator / desorbent stage 380 with subsequent heat recovery 390 which preheats the strong solution entering the generator, the subsequent expansion of the working fluid. (preferably ScC02 or supercritical ammonia) with integral energy extraction device 70 producing a low temperature expanded gas (i.e. producing cooling) within the evaporator 510. The particularly preferred embodiment integrates the AFEX and the heat pump. absorption having fluid communications at various points. The first enhancement is such that exhaust heat is recovered from condenser 545 which is used at least as part of the thermal pre-irradiation 565 used prior to heat source 360 (even necessary depending on desorption temperature). The second enhancement is such that the cooling produced by the absorption heating pump made available to AFEX through the evaporator 510 removes the need differently for mechanical cooling equipment. The third enhancement is the direct integration of a 330 power extraction device capable of handling the high solids content while simultaneously extracting energy during the rapid expansion stage. Another enhancement is the use of a pressure changer 515 after the filtration / separation membrane 60 wherein the solids are further processed by a 570 pretreatment post-process such that pressure is recovered from the pretreatment process with the untreated biomass 300 to complete the cycle.

Another significant use of electricity is the conversion of the CO2 by-product from the biomass conversion process of the fermentation (or even gasification / pyrolysis) steps. The by-product of CO2 with H2O is electrochemically reduced in methanol, which is then subsequently used as an input in the preferably integrated biodiesel esterification process. This reduction reaction is best performed within ILs, PILs, and / or LIPs due to significant electrical conductivity in combination with high CO2 absorption. An additional means for increasing electrical conductivity and reducing working fluid viscosity is by adding carbonate solvents including propylene carbonate "PC" and dimethylcarbonate "DMC". Alternatively, the absorbed CO2 may be additional carbon or carbonate synthesis as an effective energy medium for sequestering CO2.

The high electrical conductivity (and thermal conductivity which enhances heat transfer) makes the biomass solution superior for a wide range of chemical reactions particularly those enhanced by electrochemical, electrolysis, electrocatalytic, or photocatalytic process steps. Additional inclusion of nanoscale conductors and semiconductors as a means to increase the quantum mean of free path, quantum dots, copper, Fe2 + ions, iron-sulfur cluster, or electrides increases reaction rates. The digestion of organic materials can be further enhanced by electrochemical process steps.

The presence of electron donors within the biomass conversion process, particularly when electrochemical processing is used, reduces the oxidation rate of hydrolysis. Thus removing sources from electron donors prior to hydrolysis including lignin, antioxidants, polyphenols, and aromatic compounds increases the photokalitic or enzymatic oxidation rate by a minimum of 10% throughout the conversion / degradation that occurs. occurs during the fermentation of biomass solution for biofuels including ethanol and butanol. Sources of electron donors include tocopherols, antioxidants, aromatics, and the like.

Additional means for enhancing the conversion process is obtained by including at least one working fluid additive selected from the group consisting of electron transfer mediators including iron salts, iron salt derivatives, potassium salts, lactic acid salts, of potassium salts, derivatives of lactic acid salts, phytic acid, gallic acid, potassium ferricyanide, polyoxometalates, violinic acid, polycationic protein, thialotium bridge complexes, thiolated complexes, metalloproteins, protein complexes having a cluster sulfur complexes, trehalose complexes, iron sulfur cluster, sodium ammonia, sulfur ammonia, a chitosan complex including chitosan lactate, chitosan alpha lipoic acid, and thiolate chitosan, nanoscale catalyst, electrocatalyst, photocatalyst, electron donor, electron acceptor, ultraviolet absorber, infrared absorber, quantum dot, nanoscale powder, electron transfer enhancer including iron salts, iron salt derivatives, potassium salts, lactic acid salts, potassium salt derivatives, lactic acid salt derivatives, phytic acid, gallic acid and combinations thereof.

Direct integration and interdependence between the absorption heat pump, power generation capabilities, heat transfer, and numerous resulting co-products requires control systems well beyond the process requirements of traditional process conversion process. The implementation of a control system having nonlinear algorithms capable of determining the maximum operating performance in real time by monitoring at least one parameter selected from the group consisting of cost and price of electricity, cost and price per btu, cost and price per btu. emissions, carbon dioxide emission credits, cost and price of methanol per btu, cost and price of resulting biofuels per btu, electricity conversion factor for electrochemical reactions, and operating parameters of a reverse fuel cell for Electrochemical reduction of at least one component of the biomass solution results in optimization of revenue production and lower operating expenses.

Still another embodiment is the integration of an energy extraction device within the rapidly expanding stage that occurs within the burst stages (ammonia fiber burst, steam burst, supercritical burst). The result is the simultaneous production of electricity and cooling which ends the hydrolysis process. The preferred energy extraction device includes a generator rotor, pressure changer, equase turbine. These devices have the distinct advantage of allowing pressure expansion with minimal impact of biomass solids. An additional means for reducing the precipitated cellulose particle size, which also increases the surface area, utilizes a microcannister device having channels smaller than 10 microns prior to the expansion stage. A preferred embodiment utilizes a rapidly expanding stage that occurs in a series of independent pressure drop stages consisting of at least a first pressure drop stage and a second pressure drop stage. A particularly preferential pre-expansion pressure is a pressure greater than the supercritical pressure of the fluid. The first stage of pressure drop has a pressure below the critical pressure of at least one working fluid. Utilizing the minimum two pressure drop stages enables the ability to generate maximum energy (ie, transform enthalpy of thermal energy from the biomass solution into electricity) while minimizing viscosity problems associated with the gradual reduction of complete solid pressure. of post-pretreatment biomass. The second stage of depression drop occurs within a high pressure fluid pressure exchanger being the biomass solution from the pre-treatment process outlet and low pressure flow being the biomass solution prior to the pre-treatment process, such as a means to further increase the energy balance of the biomass conversion process.

Referring to Figure 9 is another embodiment that further enhances 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 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 H2 O solution. Solution 780 is prequalified 390 from the thermal energy recovered from water / liquid vapor 540 isolated by those of skill in the art including nanofiltration 60 subsequently heated by a second stage heat source360. The combined fluid is now operating in the mode of an OrganicRankine binary solution cycle having a predicted operating efficiency of about 30% while simultaneously producing pure high pressure supercritical fluid EtOH 785 which is expanded through an energy device 70 and further evaporated 510, preferably by evaporator of the aforementioned absorption heating pump.

Still another embodiment is the infusion of at least one working fluid additive selected from the group consisting of monomers, polymers solubilized in at least one working fluid, microspheres, and nanoscale powders having a particle size of less than 100 µm. -meters. Particularly preferred additives further comprise immobilized enzymes, immobilized catalysts, or combinations thereof. Superior additive distribution is achieved by mixing the slurry-additive solution with additives by at least one process intensifying mixer including hydrodynamic cavitation devices, grinding disc, and draw tube within the tube. The use of multipurpose microsferasserve including enzyme immobilization for easy reuse and enzyme recovery, reduction of post-treatment biomass solids agglomeration, reduction of 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 biomass conversion system of the invention is the subsequent processing of post-expansion desorbed carbon dioxide as a means to sequester carbon dioxide by-product including carbon dioxide polymerization media. or carbonate synthesis. Using desorbed carbon dioxide, which remains a high-pressure thermal transfer fluid, continues to have relatively low surface tension allowing chemical reactions to occur within a microreactor.30 Supercritical Working Fluids - Yet Another Characteristic

One of the biomass conversion system is the use of even ternary binary solutions, recognized in the art, having the ability to penetrate regions whereby the components of the solution range from lowly miscible to partially miscible. These variations allow low-energy methods to separate the solution within the immiscible range by simply decanting, centrifuging, or otherwise isolating the immiscible fluid components. Transition methods between the miscible and miscible range are performed by varying at least one parameter selected from the group consisting of pressure and temperature. Thus ScCO2, which is the preferred heat transfer fluid, is isolated from the biomass solution for use within the thermodynamic cycle as a means to produce heat, cooling, power, or combinations thereof with the inventive integration of the biomass conversion process with one. ScC02 absorption heating pump system. A reference working fluid for the thermodynamic absorption cycle is an ionic liquid, although an integrated background cycling absorption / desorption cycle15 is effectively performed using binary fluids consisting of at least materials selected from the group consisting of organic liquids, alcohols, ammonia, water, carbon dioxide, lithium chloride / bromide or combinations thereof.

Some particularly preferred binary fluids are supercritical fluids. The maximum pressure of the supercritical biomass solution is significantly in excess of 12.9 MPa (600 psia). The high lateral pressure is a minimum of 9.65 MPa (1400 psia) when the binary composition is isobutyl acetate or amyl acetate. Specifically preferred pressure is up to 34.47 MPa (5,000 psia) for ionic liquids having thermal stability up to 450 degrees Celsius.

Referring to Figure 2, the additional inclusion of water 120, especially when operating at a maximum pressure in excess of the required supercritical pressure for water, allows the additional benefit of increased fuel conversion rate. Therefore a specifically preferred biomass solution 30 consists of at least fluids selected from the group consisting of ionic liquids, carbon dioxide, and water. A preferred embodiment is the mixture of supercritical carbon dioxide, ionic liquid, and biomass with supercritical water. within a microchannel heat exchanger 130. Using the microchannel heat exchanger generally minimizes the particle size of the precipitated cellulose to less than about 10 microns. The reaction products are then optionally separated immediately after the micro channel reactor by separation methods known in the art 60. Another subsequent separation process occurs after the first energy extraction stage 70, which then passes through an energy extraction That in this case is ideally a pressure changer. Desorbed ScC0210 is sequestered 160 and further processed in a preferred embodiment into a high value added co-product being transformed chemically into a high throughput microchannel mixer / reactor (aka mixer / booster). 170. Alternatively or immediately before the microchannel heat exchanger is a mixture of supercritical carbon dioxide, ionic liquid, and biomass with hydrodynamic cavitation supercritical water, which also has the benefit of mixing intimately virtually instantaneously.

Absorption Cycle Integration - Solubilization of biomass at a temperature not exceeding 60 degrees Celsius allows the absorber to be "cooled" by the biomass at room temperature as a means to increase the efficiency of the low temperature and low pressure side of the biomass. absorption system. Creating such multistage effect absorption systems, as is well known in the art, further enhances both the efficiency of the absorption heating pump and the process of converting biomass to fuel.

Further integration of the absorption cycle and the biomass pretreatment process solution allows the expansion of the biomass solution to not only achieve rapid cooling for subsequent sequencing of the hydrolysis reaction, but also concurrent energy extraction. It can be either mechanical or electrical by methods known in the force generation technique. The solution is rapidly quenched by at least one process step selected from the group consisting of sequential hydrodynamic cavitation processing and supercritical biomass solution expansion, supercritical biomass solution expansion below the supercritical water pressure followed by the solution expansion step. supercritical biomass to below the supercritical pressure5 of carbon dioxide. An optional step for carbon dioxide sequestration can be obtained at various points from the beginning to the end of the biomass conversion system (a similar sequestration point is after expansion of the biomass solution below the point where there is a vapor component significant water, which is largely a function of the post-ScCO2 step as is known by the art ranging from chemical reactions producing carbonate products to polymerization.The introduction of the intermediate expansion stage allows water to be isolated from the biomass solution as an additional means for control the conversion rate of biomass to fuel.15 Separation of components within the biomass solution is

performed by means including at least one method selected from the group consisting of nanofiltration, decantation of immiscible solution components, or combinations thereof. Each expansion stage has the additional inclusion of energy extraction devices to produce mechanical or electrical energy and / or preceded respectively by filtration means as is known in the art.

A typical action plan is shown in Figure 4 which reveals the multiple areas where heat transfer fluids via heat exchangers are in fluid communication between a biomass fuel conversion pretreatment process and a heat exchanger pump system. absorption. The series of steps having heat transfer include: a) biomass is combined with ionic liquid in a 300 biomass solution; (b) pre-treatment step including increasing the temperature and pressure of the solution by thermal means 310; (c) recovery of ca-30 Ior 320 from the after-treatment solution used as at least the first stage of providing thermal energy (thermal source 360) to the absorption heat pump generator 380; d) Expansion through the energy extraction device 330 of the pretreatment solution followed by filtration / separation of the by-products 60, which may alternatively be prior to the expansion step; (ee) Heat recovery 350 of the final pretreatment biomass solution product through a 5 heat exchanger as a heat sink 420 which is used for thermal pre-irradiation of biomass as a means to reduce thermal energy requirements, and additionally preheating the biomass from the heat recovery from the absorption heat pump absorber 410 which also includes absorption heat in addition to the thermal energy transferred10 during the energy absorption / expansion cooling evaporator device 70 transferred through a heat exchanger heat exchanger. heat 370 of knowledge in the art. Absorption heat pumps, as known in the art, have a number of 390 heat recovery heat exchangers as a means to increase the Coefficient of Cooling Performance 15, including heat recovery desorbed gas pre-cooling. for strong preheating of the solution before the generator 380 is hit.

Another typical action plan is shown in Figure 5 which also reveals the multiple areas where heat transfer fluids through 20 heat exchangers are in fluid communication between a biomass fuel conversion pre-treatment process and a heat exchange pump system. absorption. The series of steps having heat transfer include: a) Biomass is combined with ionic liquid in a biomass solution 300 after being preheated by heat removed from the absorber of the thermodynamic absorption heat cycle 410 through the heat recovery decal exchanger. (heat sink 420); b) Pretreatment step including first stage of further increasing the temperature and pressure of the solution by thermal means 370 and other catalytic or enzymatic processing as a means of transforming biomass into 30 a number of by-products as is known in the art. technique for final conversion to fuel; c) The temperature of the biomass solution is further increased by thermal means 360 into the generator / desorbent 380; (d) by-products of isolated biomass pretreatment 60 of desorbed ScCO2 using means of knowledge in the art; e) heat recovery 390 from the desorbed ScC02, which serves as pre-cooling of the ScC02 subsequently transferring the thermal energy5 to the second preheat stage of the biomass solution in the pretreatment process 310; and the thermodynamic absorption cycle is completed through an expansion stage where the ScC02 converts thermal energy to mechanical or electrical energy through an energy extraction device 70 as known in the art.10 The additional integration of solar concentration and flat panel co

A thermal source with the supercritical biomass solution and a bio-catalytic step, such as including Ciba® TINOLUX® BBS in a supercritical solar concentrator (or supercritical flat solar panel) produces a highly effective and reactive photocatalytic system. The result is a hybrid photovoltaic system15 and biomass fuel, without being bound by theory, which achieves high efficiency of localized electron conversion to perform degradation of biomass oxidation.

A typical ionic liquid for the biome conversion system of the invention is the use of the same ionic liquid used in the study of ama-20 fruit hardening by high resolution CRMN spectroscopy: "greerí solvents meet green banana from Diego A Fort, Richard P. Swatlos-ki, Patrick Moyna, Robin D. Rogers, and Guillermo Moyna, received (in Columbia, MO, USA) on October 23, 2005, accepted December 15, 2005, and first published. as an Advance Article on the web on January 19, 2006, in which banana pulps at any stage have been completely dissolved, which is in IL-1-n-butyl-3-methylimidazolium chloride ([C4min] CI ILs are capable of dissolving carbohydrates ranging from simple sugars to polysaccharides Without being bound by theory, unhydrated clio rect ions solvate carbohydrates by forming hydrogen bonds30 with their oxyhydryl clusters which in turn break the intermolecular hydrogen bonding network compl It is present in many polysaccharides and promotes their dissolution. High Value Co-products - Another embodiment is a means of altering the composition of the protein fraction within the mass solution. Particularly the protein fraction is preferably hydrolysed into branched chain peptides and amino acids.

A particularly preferred pretreatment process is at temperatures where the protein fraction of the biomass solution is subjected to minimal denaturation. The use of enzymes to simultaneously hydrolyze cellulose, hemicellulose, and ligninacellulose with protein hydrolysis is a unique approach. Protein processing for hydro-10 Protein lysates, free amino acids or peptides when combined with electron transfer mediators serves the dual purpose of reducing bitterness in protein hydrolysates, free amino acids, or resulting peptides after serving the purpose of enhancing the rate of protein. hydrolysis during the pre-treatment process. This dual purpose has the added advantage of not requiring extraction of the electron transfer mediator when said electron transfer mediator is a food step ingredient.

The specifically preferred method for processing a biomass solution further comprises bitterness reducing additives having both the ability to reduce the bitter taste of free amino acids and peptides and to increase the rate of at least one selected reaction between the group. consisting of cellulose hydrolysis, protein hydrolysis, ligninacellulose hydrolysis, electrochemical reduction of biomass conversion byproducts including carbon dioxide, electrochemical chemical digestion, and electrochemical oxidation of biomass solution. Additional dual purpose additives (bitter reducing and biomass conversion enhancing additives) include trehalose (provide thermal stability to enzymes and proteins), electron transfer mediators, electron donors including lactic acid, ions minerals selected from the 30 group consisting of calcium, ferrous, cupric, manganous and magnesium (enhancing electron transfer and impacting taste receptors) .The biomass source is a raw material selected from the group consisting of dry grain of distillers with solubles, corn, grass, oats, and rice.

Still another embodiment is the isolation of protein fractions enabling membrane filtration systems to operate effectively at pressures greater than the pressure of the membrane design as a means to increase the insulation efficiency. Therefore the membrane filtration system additionally consists of a detector / controller to maintain pressure across a microfiltration membrane or nanofiltration as a means for isolating protein fractions including protein hydrolysates, amino acids, and peptides wherein the pressure across the membrane. Microfiltration or nanofiltration membrane is a pressure differential, and where the pressure differential is less than the maximum operating pressure of the microfiltration or nanofiltration membrane.

Claims (41)

1. A biomass solution consisting of a pretreatment solution, wherein the pretreatment solution comprises at least one working fluid selected from the group consisting of liquid ionic phosphates, polyammonium tonic liquid sulfonamides, and poly (liquid ionic), and combinations thereof. A biomass solution according to claim 1, wherein the working fluid additionally consists of at least one gas selected from the group consisting of carbon dioxide, ammonia, and methane. A biomass solution according to claim 1, further consisting of enzymes having at least hydrolysing function selected from the group consisting of cellulose, hemicellulose, ligninace cellulose, and protein hydrolysis. Biomass solution according to claim 3, wherein the enzymes are immobilized to at least one working fluid. The biomass solution according to claim 4, wherein the biomass solution additionally consists of microwave irradiation to increase the hydrolysis rate by a minimum of about 10% and wherein the hydrolysis temperature of the biomass solution is at least 5 degrees Fahrenheit lower than the vacuum of the microwave radiation pretreatment process. 6. A biomass solution consisting of a pretreatment solution, wherein the pretreatment solution consists of an absorption heat pump having at least one component of the working fluid in fluid communication with the pretreatment process. where at least one component of the working fluid is either the refrigerant or the absorbent coolant of the absorption heating pump, and where the name of a working fluid increases the surface area of the pre-process biomass. treatment. Biomass solution according to claim 6, wherein the absorption heat pump refrigerant removes moisture from the biomass solution. 8. Biomass solution consisting of at least one first working fluid component A1 of a biomass for biofuel conversion process in fluid communication with a sa biome for biodiesel conversion process. A biomass solution according to claim 8, wherein at least a first component of working fluid A1 is a by-product of the biodiesel conversion process including glycerine or glycerol, and reduces the biomass moisture content of the biomass for process conversion. biofuel. A biomass solution according to claim 9, further comprising a regeneration process for removing moisture from at least one first component of working fluid A1, and wherein the regeneration process utilizes exhaust heat. recovered from at least one second component of working fluid A2 in fluid communication with both biomass fuel and biomass conversion processes. A biomass solution according to claim 8, further consisting of a power generation cycle to produce electricity used for at least one function selected from the group consisting of microwave irradiation, electrochemical reduction, and electrolyte. . A biomass solution according to claim 8, further comprising an electrochemical reduction process for converting biomass carbon dioxide by-product for biofuel conversion process to an input to biomass for biofuel conversion process. A biomass solution according to claim 8, further consisting of carbonate solvents as a means of increasing electrical conductivity and at least reducing the viscosity of a working fluid. Biomass solution according to claim 12, wherein the carbon dioxide by-product is absorbed by at least one working fluid A1. A biomass solution according to claim 14, wherein the carbon dioxide by-product absorbed by at least one working fluid A1 is further processed by means including carbon dioxide polymerization reactions, carbonate synthesis, or electrochemical reduction to methane. 16. Biomass solution consisting of a pretreatment solution, wherein the pretreatment solution consists of at least one step selected from the group consisting of electrochemical, electrolysis, electrocatalytic, and photocatalytic process steps, and that the pre-treatment solution consists of at least one working fluid additive selected between the nanoscale and semi-conductor combination group as a means to increase the quantum mean free path ionic phosphates, liquid polyammonium ionic sulfo-namide phosphates, quantum dots, copper, Fe2 + ions, iron-sulfur cluster, or electrides. Biomass solution according to claim 16, further comprising a process step for removing electron donor sources prior to hydrolysis including lignin, antioxidants, polyphenols, and aromatic compounds. The biomass solution according to claim 16, further comprising at least one working fluid additive selected from the group consisting of electron transfer mediator including iron salts, iron salt derivatives, potassium salts, lactic acid salts, potassium salt derivatives, lactic acid salt derivatives, 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, sulfur ammonia, a chitosan complex including chitosan lactate, chitosan alpha lipoic acid, and chitosan thiolate, nanoscale catalyst, electrocatalyst, photocatalyst, electron donor, electron acceptor, ultraviolet absorber, infrared absorber, quantum dot nanoscale powder, electron transfer enhancer including iron salts, iron salt derivatives, potassium salts, lactic acid salts, potassium salts derivatives, lactic acid salts derivatives, phytic acid, of the Gallic and their combinations. A biomass solution according to claim 16, further comprising a control system with non-linear algorithms capable of determining the maximum temporal operation yield by monitoring at least one parameter selected from the group consisting of cost and price. of electricity, cooling cost and price per btu, heating cost and price per btu, carbon dioxide emission credits, cost and price of methanol per btu, cost and price of biofuels resulting by btu, electricity conversion factor for electro-reactions and chemical parameters, and operating parameters of a reverse fuel cell for electrochemical reduction of at least one component of the biomass solution. 20. A biomass solution consisting of a hydrolysis process, wherein the hydrolysis process is terminated within a rapid expansion step further contained within an energy extraction device including generator rotor, pressure changer, and quasi turbine, or a microchannel device having channels smaller than 10 microns as a means for reducing precipitated cellulose. A biomass solution according to claim 20, wherein the rapid expansion step occurs in a series of independent pressure drop stages consisting of at least a first pressure drop stage and a second pressure drop stage. A biomass solution according to claim 21, further comprising at least one working fluid having a pressure greater than the supercritical pressure of at least one working fluid. The biomass solution of claim 21, wherein the first pressure drop stage has a pressure below the supercritical pressure of at least one working fluid. Biomass solution according to claim 21, wherein the biomass solution is infused with at least one working fluid additive selected from the group consisting of monomers, solubilized polymers with at least one working fluid, microspheres, and powders. nanoscale having particle size smaller than 100 nanometers. The biomass solution of claim 21, wherein the biomass solution is mixed by at least one process intensifying mixer including hydrodynamic cavitation devices, draw disc, or draw tube within the tube. A biomass solution according to claim 24, wherein the microspheres additionally consist of immobilized enzymes, immobilized catalysts, or combinations thereof. A biomass solution according to claim 24, wherein the working fluid additives are further processed into polymers, copolymers, or block copolymers. A biomass solution according to claim 21, wherein the second stage of pressure drop occurs within a pressure exchanger wherein the high pressure fluid is the biomass solution at the outlet of the pretreatment process and in The low pressure fluid is the biomass solution before the pretreatment process. 29. A biomass solution consisting of a rapidly expanding pretreatment process having an expanded gas and a force generating thermodynamic cycle wherein the expanded pretreatment process gas is in fluid communication with a cyclothermodynamic condenser. force generator as a means to increase the efficiency of the thermodynamic cycle of both the biomass pretreatment process and the power generator thermodynamic cycle. A biomass solution according to claim 29, further comprising an exhaust heat recovery device for recovering thermal energy from the force-generating thermodynamic cycle condenser wherein the thermal energy is further increased by the absorption heat in the Subsequent mixing of the gas expanded by at least one absorber before recombining with the bi-mass solution. A biomass solution according to claim 30, wherein the heat of absorption is in fluid communication with the force-generating thermo-dynamic cycle as a thermal pre-irradiation stage. A biomass solution according to claim 29, further comprising a step of the exhaust heat recovery process wherein the exhaust heat is used for at least one function selected from the group consisting of preheating the process input. rapid expansion pretreatment, hydraulic heat pump, and thermal inlets of an absorption heating pump as a means to increase fluid pressure. A biomass solution according to claim 29, further comprising a leakage heat recovery device for recovering thermal energy from the force-generating thermodynamic cycle condenser in fluid communication with the biomass solution and wherein the Thermal energy is used as at least a partial thermal energy source for an endothermic reaction. The biomass solution of claim 29, wherein the force-generating thermodynamic cycle consists of a working fluid having at least one first working fluid W1 and a second working fluid W2. The biomass solution of claim 34, wherein the first working fluid W1 and the second working fluid W2 are individually selected from the group consisting of carbon dioxide, ammonia, methanol, ethanol, butanol, and water. The biomass solution of claim 29, wherein the force-generating thermodynamic cycle is selected from the group consisting of the Organic Rankine, Goswami, Kalina, and Carnot binary cycles. 37. A biomass solution consisting of a protein fraction, wherein the protein fraction is preferably hydrolyzed to branched chain peptides and amino acids. The biomass solution of claim 37, wherein the hydrolysed protein fraction in branched chain peptides and amino acids additionally consists of bitter reducing additives and has the ability to reduce the bitter taste of free peptides and amino acids, and increase the rate of at least one reaction selected from the group consisting of cellulose hydrolysis, protein hydrolysis, deligninacellulose hydrolysis, electrochemical reduction of biofuel conversion by-products including carbon dioxide, electrochemical biodigestion, and electrochemical oxidation of biomass solution. The biomass solution of claim 38, wherein the bitter reducing additives include trehalose, electron transfer mediators, electron donors including lactic acid, mineral ions selected from the group consisting of calcium, ferrous, cupric, manganous, and magnesium. The biomass solution of claim 37, wherein the biomass solution is a raw material selected from the group consisting of dry distillers grain with soluble maize, grass, oats, earroz. The biomass solution of claim 37 further comprising a detector / controller for maintaining pressure across a microfiltration or nanofiltration membrane as a means for isolating protein fractions including protein hydrolysates, amino acids, and peptides, wherein the pressure across the microfiltration or nanofiltration membrane is a pressure differential, and wherein the pressure differential is less than the operating pressure of the maximum microfiltration or nanofiltration membrane.