WO2008137989A1 - Process for manufacturing biomass based products - Google Patents

Abstract

A method of forming a bioadhesive by cavitating biomass to disrupt the cellular structure of the biomass, hydrofyzing the disrupted biomass into components, and processing the hydrolyzed components into a bioadhesive is provided. The method can also be used to form a biopoiymer or bioplastic. Also provided the bioadhestve formed by this method. A method of forming foiαpolymers by cavitating biomass to disrupt the cellular structure of the biomass and produce porous biomass fibers of differing weights and sizes, hydrolyzing some of the disrupted biomass into components, reeombming Hm hydrolyzed components with non-hydroiy^ed disrupted biomass, and adding chemicals to the combined hydroiy^eci components and non-hydrolyzed disrupted biomass thereby forming a biopclymer

Description

PROCESS FOR MANUFACTURING BIOMASS BASED PRODUCTS

BACKGROUND OF THE INVENTION

1. Field of the Invention

Generally, the present invention relates to methods, materials, formulae and devices for producing bio-adhesives, bioplastics, biopolymers, composites, bio-chemicals, construction lumber and building-materials.

2. Description of the Related Art

As attempts are being made to become ecological, people are trying to determine ways to utilize biomass, particularly in replacing petroleum in adhesives, bioplastics, biofuels and bio-composites. Numerous methods are under development for refining biomass. Once biomass has been refined, additional steps must be performed to convert the products of the refinement process into precursors for other products, and/or to combine them with specially modified forms of biomass as stand-alone bio-products or combined with petroleum-derived materials. Presently available methods to produce chemical precursors for adhesives and plastics are achieved either by gasification or more traditionally by extracting oligomers and monomers of glucose, xylose, arabinose, galactose and other trace sugars, as well as protein and amino acids, and tannins from paper pulping to be transported to adhesive production plants. In more recent times, the use of paper pulp components, typically lignin or xylose sugar hydrolyzates have been limited with more focus being placed on petroleum-based products. This is due to limited availability and excessive contaminants formed as byproducts of the harsh hydrolysis conditions typically used during hydrolysis of hemicelluloses for pulping.

A commonly used wood adhesive is phenol formaldehyde (P/F) resin. P/F is used because of its resistance to moisture and it thus has a particular value in external (outdoor) or damp environments. P/F is the leading adhesive used for the manufacture of plywood, oriented strand board (OSB) and wafer board (Sellers, 1996). The principal ingredients in P/F adhesives are phenol and formaldehyde. The formaldehyde ingredient in P/F resin is derived from methanol normally produced from natural gas. The phenol ingredient is typically manufactured from benzene and propylene via a cumene intermediate. The release of free formaldehyde during the resin manufacture is a concern from a health and safety perspective. Thus, alternative adhesives have been explored.

One alternative for phenol is lignins that have been recovered from wood, wood residues, bark, bagasse and other biomass via industrial or experimental processes Natural lignin. Lignin is a random network polymer with a variety of linkages, based on phenyl propane units. Lignin-based adhesive formulations have been tested for use within plywood, particleboard and fiberboard manufacture.

While relatively mild thermal or thermo-catalytic processing at low pressures are useful in breaking the lignin macromolecules into smaller macromolecules, lignin segments and monomeric chemicals, such procedures may cause condensation reactions producing highly condensed structures such as char and tar, rather than depolymerized lignin fragments or monomeric chemicals. Thus, to date, lignin has enjoyed limited use commercially.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a method for dissolving carbohydrate and protein while creating small, internally disrupted particles of various sizes and degrees of internal disruption, and dissolving. After the components have been formed, the components can be further processed, either individually or jointly. The processing can be performed using a range of conditions that include but are not limited to, mechanical disruption combined with heat, the addition of chemicals to mechanical disruption and heat, further disruption of processed biomass under various conditions and using known methods, and recombining solid and hydrolyzed biomass components either as dissolved or as further processed. The dissolved components can be combined with additional chemicals and process conditions to produce a wide range of bioplasties, bio-adhesives, biopolymers, composites, bio-chemicals and construction materials

Biomass is subjected to rapid pressure changes combined with all of the possible combinations outlined above, for short residence times and optionally, minimal chemical inputs, thereby disrupting and hydrolyzing the cell structure of the biomass while minimizing degradation products that can inhibit downstream fermentation processes or create offensive smells for animals being fed the treated biomass. Also provided are a device or devices and parameters for use of a device or devices for performing the method. The device includes a high shear and/or cavitating and cell structure- disrupting device disposed within the high shear and/or cavitating device for creating extreme surface area and disrupting the cell structure and exposing the internal cell. The device of present invention creates biomass particles with extreme surface area compared to other methods, and does so in a significantly more cost effective manner. The device of the present invention can also utilize nitric or other acids when mineral acids are used. The method of the present invention enables both hemicellulose and cellulose hydrolysis without the use of the cellulase family of enzymes, or optionally with cellulase enzymes after the method and methods above are applied as a pretreatment.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for disrupting the gross and primary cellular structure of biomass, creating extensive surface area, hydrolyzing the biomass with high temperatures, with and without the addition of chemicals and rendering biomass components generally referred to as "hemicellulose" and "cellulose" into its sub-components of protein and/or amino acids, oligomers or monomers of glucose and xylose, tannins, acetic acid. The method also isolates and/or uses the lignin of the biomass for adhesive and bioplastic production, while recovering minerals or ash to be used in other products. The method renders products that are amenable to further refining into chemicals, gas, adhesives, plastics, polymers, and composites, while minimizing treatment and hydrolysis times and chemical loadings, including no added chemicals in certain stages, and reducing total energy requirements in the total process of refining biomass to final product(s). This can include combining components with other catalysts, including petroleum-derived chemicals, to create advanced materials and products. For example, the processed solids can be combined with hydrolyzed components and optionally with additional chemicals, materials and methods to produce bio-adhesives, bioplastics, biopolymers, composites, bio-chemicals and construction materials. The present invention allows the ability to embed insect resistant qualities and water resistance to construction materials, including site-cut pieces of OSB, which typically loses its water protection when cut. The method of present invention includes disrupting the gross structure of biomass using high shear and/or cavitation, creating extensive surface area, producing smaller and internally disrupted particle sizes, and optionally hydrolyzing parts or all of the disrupted biomass without and with high temperatures, with and without the addition of chemicals and/or enzymes, and/or combinations of the above parameters, and optionally rendering biomass components even smaller and more porous and into dissolved or un- dissolved protein and/or amino acids, oligomers or monomers of glucose and xylose, other sugars, tannins, acetic acid, while isolating and/or using lignin and all of the biomass components above for manufacturing bioplastics bio- adhesives, bio-polymers, composites, bio-chemicals and construction materials, and recovering minerals, allowing for selective separation of products, creating new or existing combinations from each of the above, and combining components with other catalysts, including those produced from the above described biomass components, including hydroxymethyl furfural, to create advanced materials and products.

Disrupted particles may be combined at various stages of size and hydrolysis with all other components described above to create flowable adhesives and bioplastics. For example, the smallest particles derived from cavitation treatment and/or hydrolysis can be combined with dissolved biomass components, which are then pressed into native types of biomass and larger cavitation treated biomass and/or cavitated and partially hydrolyzed particles. This strengthens the final product and reduces the amount of adhesive or bioplastics required to create a strong final product. As used herein, the term "biomass" includes any organic matter (whole, fractions thereof, and/or any components thereof) available on a renewable basis, such as dedicated energy crops and trees, agricultural food and feed crops, agricultural crop wastes and residues, wood wastes and residues, aquatic plants, animal wastes, municipal wastes, and other waste materials. Additionally raw materials include, but are not limited to, cellulose-containing materials, native or treated, such as corn-fiber, hay, sugar cane bagasse, starch-containing cellulosic material such as grain, crop residues, newsprint, paper, raw sewage, aquatic plants, sawdust, yard wastes, biomass, including by not limited to pretreated biomass, components thereof, fractions thereof, and any other raw materials or biomass materials known to those of skill in the art.

Biomass is processed into increasingly smaller and internally disrupted particle sizes using high-shear and/or cavitation in devices such as the Supraton that is manufactured by Buckau-Wolf of Grevenbroich, Germany. Internal configurations within the device, including the conical tools, tooth and chamber tools and nozzle tools, can be altered to increase efficacy.

The present invention provides a method for dissolving biomass in high percentages into tannins, oligomers and monomers of glucose, xylose, arabinose, galactose and related sugars, and protein, polypeptides, amino acids, fats, lignin and minerals as separate components. When the extraction occurs at lower temperatures, the biomass components can be processed into precursors for adhesives and/or bio-plastics. Alternatively, the biomass components can be further refined into adhesives, bio-plastics, composites and construction materials.

The method of the present invention dissolves biomass to high percentages, into oligomers and monomers of glucose, xylose, arabinose, galactose and related sugars, and protein, polypeptides, amino acids, fats, lignin and minerals as separate components, and depending upon the temperature at which the extraction takes place. Downstream products that can be formed from the products of the method of the present invention include, but are not limited to, adhesives, bioplastics, ethanol, sugar alcohols, organic acids, methane and other gases, milk and beef, and other commodities for chemical, gas and hydrogen production. The method of the present invention can include numerous stages. For example, hemicellulose can be dissolved by applying high shear and/or cavitation. This can be combined with, or followed by, the application of high temperatures that can combine with plant acids produced during the treatment. Alternatively, the method can utilize a combination of mineral acid or base chemicals and high temperatures to dissolve higher percentages of hemicellulose, which can be followed by the addition of high temperatures for dissolving cellulose, or dissolving all biomass components in a single step using mild acid or base and high temperatures. Another stage can include the application of cellulase after thermal- mechanical pretreatment to hydrolyze cellulose. In addition, this stage can include the addition of chemicals in conjunction with the thermal-mechanical pretreatment to hydrolyze cellulose.

The high temperature treatment, both with and without mineral acids for dissolving hemicellulose, may be followed by enzymatic hydrolysis of cellulose. Alkali and ammonia may be substituted for acid in the above- described method.

The present invention also provides a method for efficient production of organic chemicals through direct microbial conversion of any components of biomass described above which remain treated but not yet dissolved, or for enhanced gasification of biomass. All of the inputs above are preceded or followed by and/or combined with high shear or high shear and cavitation and further combined under a range of equipment tip speeds and pressures, induced under a wide range of elevated pressures at the entrance of specially designed and sized openings, and low exiting pressure zones within systems.

In the present invention, combinations of high shear and/or cavitation, temperature and pH conditions and passageway sizes can be optimally combined in multiple sequential stages to minimize cost inputs. The present invention also provides devices, mechanical operating parameters within devices, shapes of components of such devices, passageway sizes, chemicals, chemical concentrations, pH conditions, pressures, a range of higher temperatures and residence times for performing the method described above, wherein the devices include liquid stream, high-shear, cavitating and cell structure disrupting devices within the high shear and/or cavitating devices for disrupting the cell structure and exposing valuable components within the cell to heat, chemicals and dissolving enzymes. The devices are operated at various ranges of conditions and configurations depending upon substrate used, target rates, and yields of hydrolysis needed for commercial purposes.

The present invention can utilize temperatures from ambient to in excess of 300 degrees Celsius throughout the sequence of processing, without forming as many of the degradation by-products found in the prior art methods, or reducing degradation products, or efficient extracting degradation products for marketing purposes. One advantage to the present invention is that it minimizes residence time required for dissolving hemicellulose and cellulose into glucose to convert high percentages of biomass into high quality products.

The phrases "cell disrupting device", high-shear device, or cavitation device as used herein are intended to refer to a device capable of creating extreme surface area, and under the right conditions outlined above, of disrupting the gross and primary cell wall and dissolving most components of biomass, leaving mainly undissolved or redissolved lignin, and minerals.

The device can be a single orifice through which the slurry is driven by a high-pressure pump. The device can also be a tooth and chamber tool in a rotor-stator device containing many high-pressure passageways of various shapes including square, rectangular or other shapes, or a number of round holes or orifices within a rotor-stator device, or a single stage rotor-stator type device. In a rotor-stator device, as the high-pressure slurry enters the controlled-shape passageway, such as a round orifice as one example, velocity increases as the slurry passes through the orifice. Then, the pressure of the slurry containing the biomass exceeds the vapor pressure of the slurry at the exit of the orifice, causing a violent expansion of the liquid inside and adjacent to the biomass, most of which is vaporized, thus creating high collapsing pressure. More specifically, a high-speed jet coming out of an opening generates a large velocity gradient between the jet and the ambient liquid. The large velocity gradient generates a strong vortex field and shear stress field. Low pressure is generated at the center of a vortex. The stronger the vortex the lower the pressure generated. When the pressure is below the vapor pressure of the liquid, the liquid evaporates to generate cavitation bubbles. When the cavitation bubble is carried to where pressure is higher than the vapor pressure, the bubble collapses to become liquid again. The rapid vaporization and condensation process is called cavitation. Extremely high impact pressure is generated at the final stage of collapse due to liquid surface colliding with liquid surface. It has been observed that a highspeed micro jet of supersonic speed can occur and generate extremely high pressure and temperature of short duration when the micro jet strikes a liquid surface or a solid surface. The high pressure, rather than the shear stress, is responsible for damaging of the nearby material. Cavitation is more likely to occur when jet velocity is higher and when there are gas nuclei present. Therefore, a device with many small size openings generates more cavitation bubbles and, hence, is more efficient. Within the method of the present invention, slurry exiting the nozzle encounters a vacuum created by a passing rotor traveling at 150 feet per second, or more, or in some cases, less. Following such a condition, an equally powerful compressive force collapses the bubble created. This complete sequence is cavitation and exerts tremendous stress on biomass cells contained within the slurry, in part due to the liquid inside the cells that expand during the first phase of cavitation. A wide range of shear conditions may be imposed due to the forces described, including cavitation. It may not be necessary in many applications to impose cavitation when high shear proves sufficient for energy efficient hydrolysis due to combinations of shear and pH and temperature. The right conditions of pressure drop, pH and temperature on a given biomass substrate results in disruption of the cell's structure and hydrolysis upon exiting the slurry passageway, while minimizing degradation products. In most devices imposing such conditions, an equally violent recompression of the water vapors into liquid and upon the embedded biomass causes even further cellular and gross structure destruction of the biomass. It is said that the internal temperature of cavitation "bubbles" reaches 5000 degrees, or possibly higher, for a fraction of a second. The shock wave of the cavitation recompression is very intense, and is known to destroy propellers on ships over time. The cell structure disrupting device is capable, if desired, of increasing the pressure on the entry to the nozzle or other shaped passageway and correspondingly the embedded biomass cells in elevated temperature, acidic conditions or high pH and heat swollen conditions, as an example, by increasing the speed of a slurry feed pump, or the shaft speed and correspondingly, the feet per second rate of a rotor, or "tip speed", as well as by increasing the diameter of the ring or rings. In certain nozzle devices, exit pressure can be dropped further.

The term "tip speed" in describing the workings in a rotor-stator device is defined as the rate at which a point on the rotor, of a rotor-stator device, passes a fixed point on the corresponding stator, if that pathway was laid out in a direct line and measured by feet or meters. Typical speeds for many commercial, lower-speeds, high-shear cavitation devices is approximately 50 feet per second, and as low as 40 feet per second. Even lower tip speeds occur in the inner rings of multi-staged devices wherein the tools are concentric and ever larger while attached on the same plane. Higher speed cavitation devices presently available with nozzle tools can have a tip speed of 70-160 feet per second or higher. The tip speed and hole must have a size that is based on the types of biomass that are being treated. The speed and hole size relate to the viscosity, entry particle size and solids loadings possible within the pumpable slurry. The slower speed devices typically cannot pass biomass through the 1.5mm holes when the slurry contains even low solids loadings of 2.5%, unless the biomass has been hammermilled or other type milling to extremely fine particle sizes. Often, a tooth and chamber type device is used to prepare a slurried biomass for passage through the typically smaller nozzle orifice devices. Higher tip speeds are required when nozzle holes are in the 1.5mm-2mm diameter size, in order to have sufficient pressure to force the slurried biomass through the orifice. Presently only a few machines meet such a standard, including but not limited to the Supraton and the Cavitron, which are essentially the same design in the internal working components, both of which can operate at approximately 150 feet per second of tip speed. Slower machines of the same type can potentially process biomass in a similar way, but the faster the machine, the higher percentage of solids that can be processed, contributing to a more economical process. The combinations of rotor-stator speed, shaft speed, entry pressure, pressure drop, tooth and chamber, slotted and other non-round holes, and round nozzle tools, nozzle-nozzle tools, gap and hole sizes of each tool in multi-stage devices, number of tool sets in a given machine, rate of slurry flow, particle size of biomass, solids-loadings of biomass, percentage of silica, type of biomass including different lignin percentages, temperature of slurry, residence time at elevated temperatures, number of passes through any combination of above parameters, special engineered shapes of each of the above tools, special wear designs to extend life of tools, pH conditions, chemical concentration, etc., can all be synthesized in a wide number of configurations to produce an optimized pretreatment and hydrolysis of a given type of biomass. All possible combinations can be adjusted to produce a wide range of optimal final hydrolysis rates and yields of hydrolyzed sugars, proteins, separated lignin and minerals, chemical ratios, including those resulting in near neutral or neutral pH, and when applied, ratios of cellulolytic enzymes to biomass, combinations of other types of enzymes, additives to enhance rates of hydrolysis, and methods of recycling cellulase enzymes, or to create formulated, highly digestible cattle feed or feedstock for direct microbial conversion to organic chemicals. The wide range of parameters and internal machine components described above can be optimally combined to reduce the energy and capital equipment required to reach a maximum level of cell disruption, thus reducing process costs. They also allow for optimizing the process on different types of biomass that possess varying ages, and degrees of lignin, a factor that affects resistance to treatment and hydrolysis and affects slurry viscosity. Enzyme loadings employed in their ratio to biomass are greatly reduced towards commercial levels when most biomass cells are disrupted and hydrolysis rates are increased. Lower concentrations of acid or base and ammonia in both hemicellulose and cellulose dissolving stages can be employed on many substrates, depending on the percentage of lignin present, and in some instances in some stages, no mineral acid is applied. Quality of fermentable sugars produced is increased due to shorter residence times at high temperatures, in that fermentation inhibitors are reduced, and less substrate is lost to non-fermentable products. Ratios of chemicals to slurry are minimized, and utilizing nitric and other acids as catalyst, which are compatible with stainless and common steels as compared with sulfuric acid, which is not, significantly reduces equipment costs, and nitric acid neutralized with ammonia into liquid stream ammonium nitrate becomes an ideal fertilizer for pumping back onto active grass production operations near a process plant. These are some of the benefits of the method.

In another embodiment, to prepare biomass such as rice or oat hulls, straw, hay or corn stover for further processing, dry or relatively dry biomass is first reduced to a manageable size by grinding through successively smaller hammeimill screens, finally through a .5mm v-shaped hammermill screen such as a Pratermill by Prater Industries. Wet-chopped biomass is dried or partially dried using low-grade steam from the steam generation system within the present process. Particle size consistency is of the greatest importance for smooth operation in the slurry high shear and cavitation machines downstream, and depending upon equipment employed in the slurry stage, particle sizes can be considerably larger for further processing through an early stage slurry particle reduction system. Long rogue fibers tend to slow down the slurry's passage. It is practical, as an option, to hammermill through larger screens, but re-run them through the same screens to create a more symmetrical particle with length and breadth being more consistent.

The dry-ground biomass is forced into a high temperature slurry with a high-pressure screw type injection device. The solids are further processed with an inline, mixer-grinder-pump such as those manufactured by IKA. Hot slurry water, containing oligomeric and monomelic sugars, tannins, and protein from a previous hydrolysis step, is looped in the hydrolysis process, such that the return water can be utilized from a step for extracting protein prior to hemicellulose and cellulose hydrolysis. Extracting protein is an important step prior to hydrolysis. Protein is dissolved in high temperature conditions combined with acid. Protein combines with sugars being produced that become "caramelized" in a Maillard reaction, thus a loss of sugars and protein takes place. Thus the slurry is first subjected to high temperature extraction and coagulation; or exposure to protease enzymes, potassium chloride, mild acid; combinations of these; or a sequence of these as necessary to remove protein from biomass when present. Once optimal protein has been extracted, the slurry is centrifuged, the supernatant is recycled as feed water, and the proteins are otherwise extracted from the supernatant.

Optionally, at, this stage, the temperature of the slurry may be increased to between 140-230 degrees centigrade using a jacketed oil bath and/or direct steam injection, without adding a mineral acid, or a mineral acid can be added between .024%-3% concentrations to the water, depending on whether the objective is to hydrolyze the hemicellulose without dissolving the cellulose, or whether the objective is to dissolve both hemicellulose and cellulose.

A mixer-grinder-pump is a high shear, rotor-stator device capable of mixing, pumping and grinding high solid content slurries, to prepare for subsequent stages requiring small entry-level particle sizes, in single stage or multi stage devices, which can in some cases but modified versions of the mixer-grinder pump. The inline mixer-grinder pump reduces particle size sufficiently to allow smooth passage through a finer sized nozzle device with holes small enough to induce extreme shear and/or cavitation, preferably below 2mm in size, but can be larger depending on overall conditions. Examples of this type of device are the HED™ manufactured and marketed by lka Works, Inc. of Wilmington, N.C. Custom designs based upon multistage Supraton type machines, using larger slots or round holes can produce very fine and disrupted particles from longer field chopped fibers. The inline mixer-grinder pump can have conical or tooth and chamber or square or rectangular type tools, and can also have nozzle tools larger than 2mm to induce even greater shear than the tooth and chamber design tools to prepare for additional treatment under the most intense shear and cavitation conditions in single or multi-stage devices.

Once biomass has been adequately reduced in particle size employing one or more of the tools and methods described above, the slurry is passed through a high-shear or high shear and cavitating device with nozzle holes typically less than 2mm in diameter, preferably at tip speeds of approximately 150-160 feet per second. This step may be repeated, depending upon the type of biomass being treated, specifically related to lignin content and, in some cases, silica content. As the biomass slurry is pumped under pressure into the high shear or cavitation tools' chamber by the mixer-grinder-pump, it encounters one or multiple concentric layers of the tools in the chamber as the slurry is forced out radially. The pressure on the slurry creates the lateral radial force as it is pumped into the chamber by the mixer-grinder-pump and by the centrifugal force created by the spinning rotor. The slurry passes through the gaps between the teeth or through the nozzle as the rotor spins past the gaps or nozzles of the stator. In multi-stage designs, the result is a pulsing flow with a rapid succession of compressive and cavitational, expansion-compression forces. The lignocellulosic material in the slurry is subjected to these repeated forces, as the centrifugal force accelerates it through the gaps and holes toward the outer edge of the chamber. As the slurry moves towards the outer edge of chamber the centrifugal forces increase, thus intensifying the forces generated in the gaps. In the outer ring or rings, the slurry is forced through a gap or nozzle tool at the highest pressure within the system. The pressure is released upon the slurry containing the biomass as it exits the nozzle or nozzles, and results in a violent shear upon, and/or cavitation from without and within the gross and primary cellular structures of the biomass, depending on prescribed conditions. The repeated compressive and decompressive forces create bubbles by way of cavitation in the slurry within extremely intensive energy zones. The heated lignocellulosic gross fibrous structures, and most importantly, the primary cells, are pounded from the outside and blown apart from the inside by the cavitational forces, as the heated water violently vaporizes from within the gross cellular structures and then just as violently re-collapses into liquid with the passing of a rotor. It is calculated that as many as half a billion such events occurs per second in a large-scale cavitation device. Amorphous hemicellulose components are quickly disrupted and dissolved under the temperature and pH conditions outlined above.

In one embodiment, the slurry pH is not adjusted downward with mineral acid, but plant acids produced by the combination of surface area and heats lower the pH as they are formed, thus dissolving most or all of the plant's hemicellulose. In this sequential hydrolysis first of hemicellulose, then cellulose, after centrifugation of solids from the hemicellulose sugar- containing supernatant, the slurry pH is adjusted with any suitable acid at less than 1% concentration wt/wt to slurry, preferably employing nitric, sulfuric or other acid, then the slurry is optionally pumped through the cavitating device one or more times during a few seconds to five or even ten minute residence time, depending upon temperature and type of biomass. Residence time is determined by the type of biomass being treated, as it relates to lignin content and when relevant, silica content, pH and corresponding ratios of acid, temperature, final yields for commercial purposes, and of great importance, residence time is related directly to minimizing or preventing production of fermentation inhibitors, including but not limited to furfurals.

One special application of the above-described methods is for treatment of raw, untreated sewage solids and liquids. In a preferred embodiment, settled sewage solids extracted from conventional sewage settling ponds are processed as described above, after optionally centrifuging solids concentration from a typical 3% to any level in which slurry may still flow through the cavitation device. Subsequently, the solids may be concentrated to a higher level before applying heat, and when appropriate, chemicals. Supernatant from settling ponds may be filtered to capture other small sized solids for processing, with remaining supernatant being processed with conventional methods or channeled through natural or man-made wetlands, which can remediate BOD and other contaminants into benign biomass through uptake. Such biomass may then be processed as outlined above to ensure smooth system operation. Employing methods described above, treated biomass can be converted to organic chemicals by means of direct microbial conversion employing selected organisms.

Another embodiment is enhancing production of "syngas" through high temperature pyrolysis, or gasification. Another embodiment of the present invention is blending final biomass products with plastics to create unique structural materials including railroad ties, body parts, and building materials, to name a few.

In another embodiment, the methods described above are employed in which the slurry is first passed through progressively smaller holes, then is passed through a cavitation device in which heat, and optionally, low levels of acid are applied based on the level of lignin in the biomass. Within seconds of passing through the cavitation device in which heat and optionally chemicals are added, the slurry is passed through yet another cavitation device, taking advantage of rapidly dissolving biomass to further break down the biomass. The number of cavitation devices through which the hot slurry is passed to achieve theoretical or near theoretical hydrolysis is determined by the level of lignin within the native biomass. It is anticipated that many forms of biomass will dissolve to a very high degree in under 1 minute employing this strategy. This method also provides for recycling the sugar water produced in the above described fashion, to which fresh biomass may be added. This results in a higher concentration of final fermentable sugars, overcoming one of the major known obstacles in biomass refining to sugars and ethanol. Higher surface area provides the basis for heat transfer compared to larger pieces of biomass, thus accelerating hydrolysis reactions. After an effective structural attack on biomass creating extreme surface area, the rate of hemicellulose and cellulose hydrolysis into fermentable sugars or into biochemicals by direct microbial conversion is extremely fast and highly complete with relatively low chemical or enzyme weight ratios to the biomass, or lower temperatures and shorter treatment times with heat, or even shorter times with higher temperatures

Combining a cost-effective treatment of biomass with lower cost enzymes, or high temperature with minimal or no mineral pH-lowering chemicals or plant acids, or combinations of those, industrial sugars, ethanol and other biochemical production cost estimates can rapidly drop into more practical commercial levels.

For example, hydrolysis can be achieved in biomass slurry by applying temperatures of 160°C to 300°C in a one or a two-stage process. The method can also include applying high shear or cavitation using inline homogenizer devices, without applying chemicals, to achieve a percent hydrolysis of between 25%-52%, consisting primarily of hemicellulose components. The remaining (non-hydrolyzed) solids may be extracted after hemicellulose hydrolysis and separated for further treatment, fed to ruminant animals, or dissolved with cellulase enzyme cocktails. Alternately, the solids can remain in the slurry as the slurry temperature is increased. The slurry can be subjected to high shear and/or cavitation. Additionally or alternatively, the slurry can be treated with or without the addition of acid or base mineral chemicals and ammonia or ammonium hydroxide. The temperature can be set as high as 275 degrees centigrade, which is the ideal temperature for the production of adhesives using catalysts on dissolved biomass components. Alternatively, after initial treatment with related high shear and/or cavitation machines, slurry solids can be concentrated to a high degree by removing water. The water can be removed by adding energy and controlling pressure applied to the slurry, in an amount sufficient to produce steam. The slurry can then be dissolved using the methods described herein.

The present invention provides a method for harnessing the energy created downstream in the process as the energy input for hydrolysis. The temperature of the slurry is raised to a temperature at which high value products can be manufactured. This is accomplished by combining feedstock, such as oligomers, tannins, and amino acids or protein/amino acids, with various catalysts, such as bases, acids and formaldehydes, to name a few. The combination of the hydrolysis process(s) can optionally be further enhanced by utilizing a high temperature, steam production system such as those manufactured by KMW Energy of London, Ontario, Canada. When utilizing such a system, the energy is typically cycled between low pressure and temperature to high pressure and temperature, which provide the energy for hydrolysis. The hydrolysis slurry may be spray dried at various high temperatures as needed to separate solids from slurry water. During spray drying the water remaining in the biomass slurry is boiled into steam by a combination of heat and pressure management. The steam created by the method drives the electricity production turbines and piston systems, thereby driving the mechanical systems within the process, including the shear and cavitation devices.

One example of this subjects biomass of all types, including rice hulls and rice straw, to high shear and/or cavitation at temperatures as high as 200- 275 degrees centigrade while applying either no mineral acids or base, and/or applying mineral acids or base either in sequence to a residence time of seconds to 30 minutes or greater. When mineral acids or bases are applied, hydrolysis is combined with inputs, which produce adhesives with or without the additional of formaldehyde and other chemicals traditionally used in production of adhesives. In one embodiment, hydrolysis is induced by applying the conditions above, followed with a spray drying to reduce water content to 45%, with the water being driven off by the addition of energy to increase the temperature while pressure conditions allow water to boil off as high-pressure steam. The steam is then used to drive mechanical devices for electrical production, and/or to drive steam engines for turning mechanical devices described herein, or for re-using the energy within the process, including drying wet native biomass prior to processing. Adhesive production is preferably carried out with moisture contents of approximately 45%. In some processes, higher water content can be utilized followed by water removal by adding heat and controlling pressure to create steam from water associated with the product.

Subsequent steps include treating the separated solids, containing primarily glucose, lignin and minerals with an acid in concentrations less than 1%, while treating with the high-shear, cavitating device at 160°C-300°C. Alternately, an alkaline chemical may be employed at the same temperatures. This dissolves the remaining biomass and converts it to adhesive and bioplastic precursors. Alternately, this step is practiced as a single stage hydrolysis and conversion to adhesive and bioplastics precursors.

Dissolved biomass components may be combined with various sized particles produced with cavitation. Cavitated biomass particles can be subjected to steps described above, wherein times, chemical loadings and temperatures are controlled in order to produce a wide range of select gross particle sizes. In one embodiment, the smallest particles can be combined with adhesive precursors to create a viscous slurry, which is then mixed with first stage and then cavitated by undissolved biomass particles. The viscous slurry is pressed into a pressed volume of undissolved particles, then heated and dried, to produce a strong, waterproof structural or insulating material for construction, or as a bioplastic with many uses. The range of chemical composition and combinations with different size particles is wide and flexible. As the process can separate different biomass components, the adhesive or bioplastic precursor materials being produced can exhibit differing binding and other characteristics.

When a lower viscosity component created by this process is embedded within the porous structure of a biomass particle the plastic binds with not only chemical sites, but also locks within the structure of the undissolved or partially dissolved particle structure. When a low cost body of these particles are pressed and then impregnated with the various "slurries," which can contain within much smaller particles that also become a bound matrix, a strong, effective material and materials can be created. The material is manufactured at a lower cost than existing products by maximizing the amount of low cost biomass relative to the dissolved components from biomass.

The above description is that of the current embodiment of the invention. Various alterations and changes can be made without departing from the spirit and broader aspects of the invention as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law including the doctrine of equivalents. Any reference to claim elements in the singular, for example, using the articles "a," "an," "the" or "said," is not to be construed as limiting the element to the singular.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. A method of forming a bioadhesive by: cavitating biomass to disrupt the cellular structure of the biomass; hydrolyzing the disrupted biomass into components; and processing the hydrolyzed components into a bioadhesive.

2. The method of claim 1, further including subjecting the biomass to additional treatments during cavitation.

3. The method of claim 2, wherein said further treatment selected from the group consisting essentially of high temperatures, application of chemicals.

4. The method of claim 1 , wherein said processing step includes further refining the biomass.

5. The method of claim 4, wherein further refining includes applying a treatment selected from the group consisting essentially of high temperatures, application of chemicals.

6. The method of claim 1, further including combining the processed components to formulate the bioadhesive.

7. The method of claim 6, wherein said combining step includes adding materials to form the bioadhesive.

8. The method of claim 6, wherein said combining step includes adding chemicals to form the bioadhesive.

9. A bioadhesive formed by the method of claim 1.

10. The bioadhesive of claim 9, wherein said bioadhesive has insect resistant qualities and water resistance qualities.

11. A method of forming a bioplastics and biopolymers by: cavitating biomass to disrupt the cellular structure of the biomass; hydrolyzing the disrupted biomass into components; and processing the hydrolyzed components into a biopolymer or bioplastic.

12. The method of claim 11, further including subjecting the biomass to additional treatments during cavitation.

13. The method of claim 12, wherein said further treatment selected from the group consisting essentially of high temperatures, application of chemicals.

14. The method of claim 11 , wherein said processing step includes further refining the biomass.

15. The method of claim 14, wherein further refining includes applying a treatment selected from the group consisting essentially of high temperatures, appl ication of chemicals.

16. The method of claim 11, further including combining the processed components to formulate the biopolymer or bioplastic.

17. The method of claim 16, wherein said combining step includes adding materials to form the biopolymer or bioplastic.

18. The method of claim 16, wherein said combining step includes adding chemicals to form the biopolymer or bioplastic.1

19. A biopolymer or bioplastic formed by the method of claim 11.

20. A method of forming biopolymers by: cavitating biomass to disrupt the cellular structure of the biomass and produce porous biomass fibers of differing weights and sizes; hydrolyzing some of the disrupted biomass into components; recombining the hydrolyzed components with non-hydrolyzed disrupted biomass; and adding chemicals to the combined hydrolyzed components and non-hydrolyzed disrupted biomass thereby forming a biopolymer.