Patent Application
20120184721
The present invention relates to an apparatus for separating components of a solid feedstock and a method for using the same. The apparatus feeds the solid feedstock in one direction and provides a reaction fluid in an opposite direction of the solid feedstock to rapidly separate various components from the solid feedstock.
Natural cellulosic feedstocks typically are referred to as “biomass”. Many types of biomass, including wood, paper, agricultural residues, herbaceous crops, and municipal and industrial solid wastes derived from crops have been considered as feedstocks for the manufacture of a wide range of goods. These biomass materials consist primarily of cellulose, hemicellulose, and lignin bound together in a complex gel structure along with small quantities of extractives, pectins, proteins, and ash. Due to the complex chemical structure of the biomass material, microorganisms and enzymes cannot effectively attack the cellulose without prior treatment because the cellulose is highly inaccessible to enzymes or bacteria. This inaccessibility is illustrated by the inability of cattle to digest wood with its high lignin content even though they can digest cellulose from such material as grass. Successful commercial use of biomass as a chemical feedstock depends on the separation of cellulose from other constituents.
The possibility of producing sugar and other products from cellulose has received much attention. This attention is due to the availability of large amounts of cellulosic feedstock, the need to minimize burning or landfilling of waste cellulosic materials, and the usefulness of sugar and cellulose as raw materials substituting for oil-based products. Other biomass constituents also have potential market values.
The separation of cellulose from other biomass constituents is difficult, in part because the chemical structure of lignocellulosic biomass is so complex. See, e.g., ACS Symposium Series 397, “Lignin Properties and Materials”, edited by G. W. Glasser and S. Sarkanen, published by the American Chemical Society, 1989, which includes the statement that “[L]ignin in the true middle lamella of wood is a random, three-dimensional network polymer comprised of phenylpropane monomers linked together in different ways. Lignin in the secondary wall is a nonrandom two-dimensional network polymer. The chemical structure of the monomers and linkages which constitute these networks differ in different morphological regions (middle lamella vs secondary wall) different types of cell (vessels vs fibers) and different types of wood (softwoods vs hardwoods). When wood is delignified, the properties of the macromolecules made soluble reflect the properties of the network from which they are derived.” The separation of cellulose from other biomass constituents is further complicated by the fact that lignin is intertwined and linked in various ways with cellulose and hemicellulose both of which are polymers of sugars. Thus there is a need for systems and methods for separating solid biomass (such as lignocellulosic biomass) into its constituent components and treating the components to make useful products. These and other needs are addressed by the present invention.
Some aspects of the invention provide methods for separating components of a lignocellulosic solid feedstock into a concentrated lignin and a carbohydrate composition that is substantially lignin free. In some embodiments, such methods include the steps of:
introducing a lignocellulosic solid feedstock into an counter current extraction apparatus, wherein the counter current extraction apparatus comprises a proximal end and a distal end, and wherein the solid feedstock is introduced at or near the proximal end of the counter current extraction apparatus;
In other embodiments, the slurry mixture comprises a concentrated lignin and a carbohydrate composition that is substantially free of lignin.
Yet in other embodiments, the counter current extraction apparatus further comprises:
The counter current extraction apparatus can also include a feeder to supply the lignocellulosic solid feedstock to the threaded shaft, wherein the lignocellulosic solid feedstock from the feeder first contacts the threaded shaft at a first reaction zone segment that is closest to the first end of the shaft.
Still in other embodiments, the extraction fluid comprises a non-aqueous solvent system. In some instances within these embodiments, the non-aqueous solvent system comprises an organic solvent. Typically, the organic solvent comprises an alcohol such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, etc., a ketone such as acetone, an ester such as ethyl acetate, ether such as diethyl ether, tetrandrofuran, etc, or a mixture thereof.
The extraction fluid typically comprises a low concentration of acid. Suitable acids include a mono- and di-carboxyic acids (e.g., acetic acid, oxalic acid, lactic acid, malic acid, succinic acid, fumaric acid, etc.), hydrochloric acid, sulfuric acid, phosphonic acid, phosphorous acid, etc. The amount of acid present is such that the pH of the extraction fluid is typically pH 6.5 or less, often pH 6 or less, more often pH 5.5 or less, and most often pH 5 or less. Alternatively, pH of the extraction fluid within the counter current extraction apparatus is maintained at pH 5 or less, typically pH 2 or less, often pH 1 or less, and most often pH 0.3 or less. In some particular embodiments, the pH of the extraction fluid within the counter current extraction apparatus is maintained at pH 2, typically pH 1, and often pH 0.3. In some embodiments, a plurality of acid injection system is provided within the counter current extraction apparatus to allow for adjustment(s) of pH as the reaction proceeds along the length of the counter current extraction apparatus.
The resulting separated carbohydrate solution typically includes 50% or less, often 25% or less, more often 15% or less, and most often 10% or less of the theoretical lignin.
It should be appreciated that the carbohydrate solution can include separated cellulosic material, oligomeric carbohydrates, mono-, di-, and other small carbohydrates.
Other aspects of the invention provide methods for at least partially separating components of a lignocellulosic solid feedstock. Such methods typically include:
In some embodiments, at least partially separated components comprise a separated concentrated lignin. The separated concentrated lignin can be a solid lignin, a fluidized lignin, or a mixture thereof.
At least partially separated components can also comprise a separated concentrated carbohydrate.
In some embodiments, one or more additional extraction fluid is introduced in the counter current extraction apparatus between the distal and proximal ends. Typically, the additional extraction fluid has a different composition than the extraction fluid introduced at or near the distal end.
The possibility of producing sugar and other products from cellulose has received much attention. This attention is due to the availability of large amounts of cellulosic feedstock, the need to minimize burning or landfilling of waste cellulosic materials, and the usefulness of sugar and cellulose as raw materials substituting for oil-based products. Natural cellulosic feedstocks typically are referred to as “biomass.” Many types of biomass, including wood, paper, agricultural residues such as corn stover, herbaceous crops, and municipal and industrial solid wastes, have been considered as feedstocks. These biomass materials primarily consist of cellulose, hemicellulose, and lignin bound together in a complex gel structure along with small quantities of extractives, pectins, proteins, and ash. Due to the complex chemical structure of the biomass material, microorganisms and enzymes cannot effectively attack the cellulose without prior treatment because the cellulose is highly inaccessible to enzymes or bacteria. This inaccessibility is illustrated by the inability of cattle to digest wood with its high lignin content even though they can digest cellulose from such material as grass. Successful commercial use of biomass as a chemical feedstock depends on the separation of cellulose from other constituents.
The separation of cellulose from other biomass constituents remains problematic, in part because the chemical structure of lignocellulosic biomass is not yet well understood. Lignin in the secondary wall is a nonrandom two-dimensional network polymer. The chemical structure of the monomers and linkages that constitute these networks differ in different morphological regions (middle lamella vs. secondary wall), different types of cell (vessels vs. fibers), and different types of wood (softwoods vs. hardwoods). When wood is delignified, the properties of the macromolecules made soluble typically reflect the properties of the network from which they are derived.
The separation of cellulose from other biomass constituents is further complicated by the fact that lignin is intertwined and linked in various ways with cellulose and hemicellulose. In this complex system, it is not surprising that the “severity index” commonly used in data correlation and briefly described below, can be misleading. This index has a theoretical basis for chemical reactions (such as hydrolysis) involving covalent linkages. In lignocellulose, however, there are believed to be four different mechanisms of non-covalent molecular association contributing to the structure: hydrogen bonding, stereoregular association, lyophobic bonding, and charge transfer bonding. Bonding occurs both within and between components. As temperature is increased, bonds of different types and at different locations in the polymeric structure will progressively “melt,” thereby disrupting the structure and mobilizing the monomers and macro-molecules.
Many of these reactions are reversible, and on cooling, re-polymerization can occur with deposits in different forms and in different locations from their origins. This deposition is a common feature of various conventional high temperature cellulosic biomass separation techniques. Furthermore, at higher temperatures in acid environments, mobilization of lignin is in competition with polymer degradation through hydrolysis and decomposition impacting all lignocellulosic components. As a result, much effort has been expended to devise “optimum” conditions of time and temperature that maximize the yield of particular desired products. These efforts have met with only limited success.
Known techniques for the conversion of biomass directly to sugar or other chemicals include concentrated acid hydrolysis, weak acid hydrolysis and pyrolysis processes. These processes are not known to have been demonstrated as feasible at commercial scale under current economic conditions or produce cellulose as either a final or intermediate product.
Conventional processes for separation of cellulose from other biomass components include processes used in papermaking such as the alkaline kraft process most commonly used in the United States and the sulphite pulping process most commonly used in central Europe. There are additional processes to remove the last traces of lignin from the cellulose pulp. This is referred to as “bleaching” and a common treatment uses a mixture of hot lye and hydrogen peroxide. These technologies are well established and economic for paper making purposes, but have come under criticism recently because of environmental concerns over noxious and toxic wastes. These technologies are also believed to be too expensive for use in production of cellulose for use as chemical raw material for low value products.
The use of organic solvents in cellulose production has recently been commercialized. These processes also are expensive and intended for production of paper pulp.
Many treatments have been investigated which involve preparing crude cellulose at elevated temperature for enzymatic hydrolysis to sugar. Investigators have distinguished particular process variations by such names as “steam explosion,” “steam cooking,” “pressure cooking in water,” “weak acid hydrolysis,” “liquid hot water pretreatment,” and “hydrothermal treatment”. The common feature of these processes is wet cooking at elevated temperature and pressure in order to render the cellulosic component of the biomass more accessible to enzymatic attack. In recent research, the importance of lignin and hemicellulose to accessibility has been recognized.
Steam cooking procedures typically involve the use of pressure of saturated steam in a reactor vessel in a well-defined relationship with temperature. Because an inverse relationship generally exists between cooking time and temperature, when a pressure range is stated in conjunction with a range of cooking times, the shorter times are associated with the higher pressures (and temperatures), and the longer times with the lower pressures. As an aid in interpreting and presenting data from steam cooking, a “severity index” has been widely adopted and is defined as the product of treatment time and an exponential function of temperature that doubles for every 10° C. rise in temperature. This function has a value of 1 at 100° C.
It is known that steam cooking changes the properties of lignocellulosic materials. Work on steam cooking of hardwoods by Mason is described in U.S. Pat. Nos. 1,824,221; 2,645,633; 2,294,545; 2,379,899; 2,379,890; and 2,759,856. These patents disclose an initial slow cooking at low temperatures to glassify the lignin, followed by a very rapid pressure rise and quick release. Pressurized material is blown from a reactor through a die (hence “steam explosion”), causing defibration of the wood. This process results in the “fluffy,” fibrous material.
More recent research in steam cooking under various conditions has centered on breaking down the fiber structure so as to increase the cellulose accessibility. One such pretreatment involves an acidified “steam explosion” followed by chemical washing. This treatment may be characterized as a variant of the weak acid hydrolysis process in which partial hydrolysis occurs during pretreatment and the hydrolysis is completed enzymatically downstream. One criticism of this technique is that the separation of cellulose from lignin is incomplete. This makes the process only partially effective in improving the accessibility of the cellulose to enzymatic attack. Incomplete separation of cellulose from lignin is believed to characterize all steam cooking processes disclosed in prior art.
Advanced work with steam cooking in the United States has been carried out at the National Renewable Energy Laboratory in Golden, Colo. See, for example, U.S. Pat. Nos. 5,125,977; 5,424,417; 5,503,996; 5,705,369; and 6,022,419, which are issued to Torget, et al. and are incorporated herein by reference in their entirety. Processes disclosed in these patents generally involve the minimization of acid required in the production of sugar from cellulose by acid hydrolysis in processes that may also include the use of cellulase enzymes. These patents teach the use of an acid wash of solids in the reaction chamber at the elevated temperature and pressure conditions where hemicellulose and lignin are better decomposed and mobilized. The use of acid is tied to the goal of sugar production by hydrolysis.
A common feature of acid hydrolysis, acid pretreatment, and chemical paper pulping is the generation of large quantities of waste chemicals that require environmentally acceptable disposal. One proposed means of waste disposal is as a marketable byproduct. Thus wallboard has been suggested as a potential use for the large quantities of gypsum produced in acid hydrolysis and acid pretreatment. This potential market is believed illusory since the market for cheap sugar is so vast that any significant byproduct will quickly saturate its more limited market.
Some have attempted to develop processes to provide low cost cellulose for subsequent conversion to glucose sugar by enzymatic hydrolysis. However, the presence of lignin in cellulosic biomass increases dramatically the amount of enzyme needed, thereby imposing unacceptably high conversion costs. Furthermore, enzymatic hydrolysis of cellulose to sugar can be time consuming and labor intensive. More significantly, economics demand a process by which sugar can be produced for only a few cents per pound. Mainstream scientific and engineering efforts to utilize lignocellulosic biomass have been unable to achieve this goal over several decades. The challenge is to find a process that solves or avoids the problems of cost, chemical wastes, the clean separation of lignocellulosic components, and the unwanted degradation of said components.
An improved apparatus is described for counter-flow extraction of materials including, but not limited to, the separation of cellulose fibers from other constituents of lignocellulosic biomass such as found in trees, grasses, shrubs, agricultural waste, and waste paper for use in the manufacture of paper, plastics, ethanol, and other chemicals. This apparatus integrates continuous, multiple processing steps that can include chemical reactions with mixing at elevated temperature and/or pressure, filtration at elevated temperature and/or pressure, controlled discharge of liquid and solid products, steam explosion, and energy recuperation. In some aspects, the apparatus and the method of the invention can be used to produce desired components from a lignocellulosic biomass feedstock, i.e., feestock.
Embodiments of an apparatus according to the invention can include one or more twin-screw extruders used as physio-chemical reactors for processing a solid feedstock, such as solid organic biomass. Means are provided for feeding the feedstock into the extruder. Embodiments of the apparatus include a twin screw extruder having cavities formed by the interlocking screws, and these cavities progress through the extruder barrel carrying with them the feedstock. Reaction/retention time may be determined by the pitch of the screws, the rotation rate of the screws, and the length of the screws in the barrel.
Screws can be configured for different functions in different parts of the reactor. Long pitch screws with cavities loosely filled are used for transport of the feedstock while reactions occur. If the screw pitch is decreased progressively over a distance of a few screw diameters, feedstock in the cavities will be compressed to produce a tight dynamic plug at this short pitch location. Beyond the plug location, long pitch screws will again have their cavities loosely filled. The plugs will be dynamic with fresh feedstock being continuously forced into the plug zone and compressed plug material being continuously broken up as it progresses into the following long-pitch zone. Plug formation involves large shearing forces that decompose fibrous feedstock, thereby reducing energy needed for feedstock preparation and making it more susceptible to chemical processing.
Two plugs can be formed at different locations along the extruder length to create a reaction zone between them. The plugs can be made tight enough to contain up to about one thousand psi of pressure or more if the desired physio-chemical processing should so require. The apparatus may include a plurality of plugs, (e.g., two or more plugs). Additional plugs can be formed so that the feedstock material progresses through a sequence of processing steps. The plugs can easily reduce moisture content to 50% as the feedstock passes through them. Thus the plugs serve not only as separators between reaction zones, but they can also supplement (or substitute) for the role played by filters in separating liquids from solids between processing steps.
Dimensional tolerances in a quality twin-screw extruder may be small, allowing for the continuous counter-flow of liquid reactants against the direction of movement of the feedstock solids. In the counter-flow operation, feedstock component particles larger than the dimensional tolerance are carried in the screw cavities, while the liquid flows through the cracks in the opposite direction. Counter-flow provides a highly efficient mode of extraction that may be combined with chemical reactions by providing suitable reagents in the liquid. In some embodiments, a “reaction zone” may be a counter-flow water wash to remove residual chemicals from a previous physio-chemical reaction zone. In additional embodiments, a reaction zone may employ co-flow or plug flow by positioning liquid input and discharge ports. Some feed materials may not require continuous screws in transport zones. A plurality of alternations along the barrel between screws and no screws will allow controlled compaction of material thereby increasing residence time and reducing capital costs per unit of throughput with only modest increase in counter-flow pressure drop.
In a continuous counter-flow reaction zone, liquid must be discharged while retaining solids in the reactor. This can be a problem since the counter-flowing liquid can carry with it any particles smaller than the dimensional tolerances of the screw/barrel system. These small particles in combination with the larger particles at the position of liquid discharge may clog a static filter system. The solution to this problem is a self-cleaning, dynamic filter system comprising a miniature, twin-screw extruder that forces solids back into the main reaction zone while allowing liquid (with its load of fine particles) to discharge in counter-flow. The combination of “dewatering” action by the dynamic plug and dynamic filtration of discharging liquid provides in situ solid/liquid separation equivalent to conventional filtration.
Applications of the invention include operation at elevated temperature and/or pressure. In some of these applications, neither liquid nor solids are discharged directly to atmospheric pressure without upsetting reaction zones or plugs, as a portion of the discharging material flashes to vapor. Pressure may be maintained and controlled as the material is discharged, but spring loaded devices commonly used for this purpose can clog with the particulates in the two-phase slurry discharges. The clogging problem may be addressed in the present invention with a variety of techniques.
In one technique, material can be discharged in bursts by means of a system of two valves preceded by a hydrolyic accumulator. In this system, discharging material is accumulated with a concomitant increase in pressure. When the pressure reaches a set point, the first valve is opened briefly to fill the space between the valves. The second valve is then opened briefly with compressed air being used to blow material out of the space between the valves. The valve action results in a pressure drop in the accumulator determined by the relative free volume in the accumulator and the volume in the space between valves. Discharging material again builds pressure in the accumulator and the cycle repeats. This discharge system is especially useful when flashing of the discharged material is required or desired as a feature of the overall biomass processing.
In another technique, material can be discharged continuously and controllably by use of a positive displacement pump run in reverse with speed regulated by pressure in the reaction zone. Piston pumps, gear pumps, and progressing cavity pumps may all be used with the systems and apparatuses of the invention. Discharging material may first be cooled by, for example, heat exchange and/or dilution with a cold liquid stream.
The twin-screw extruders may include a plurality of reaction zones with a plurality of reaction times. If a single extruder is long enough to experience bending and twisting under torque, the same number and length of reaction zones may be accommodated by two or more separate extruders that are coupled together. This limits the screw length of any one extruder while retaining the advantages of a single pressurized vessel with multiple, interconnected, reaction zones.
Another advantage of the invention is that the temperature in a counter-flow reaction zone need not be uniform. This can be used when the apparatus or system is being used, for example, to extract hemicellulose from biomass. Hemicellulose is mobilized by hydrolysis of the natural hemicellulose polymer. The soluble sugar monomers and oligomers formed are subject to further decomposition to undesirable products, and this is a serious limitation in batch or plug-flow processing. In the apparatus of the present invention, a temperature gradient can be established such that the solids being processed progress into continuously more severe conditions while the mobilized sugars in counter-flow are carried into continuously less severe conditions thereby minimizing further degradation.
The present invention relates to apparatus having a variety of features that may be convenient and/or necessary for the processing of biomass or other material to produce intermediate products having a variety of applications as feedstock in the production of finished goods. The various features can be used in a variety of configurations and combinations to meet particular processing needs. To illustrate aspects of the invention, an embodiment of an apparatus according to the invention will be described which is called a process development unit (PDU).
A simplified schematic of the PDU is shown in
Referring again to
In some embodiments, the countercurrent rinse fluid includes water, acid, bases, organic solvents, inorganic solvents, cellulose solvent, lignin solvent, ionic liquids, other fluid that is commonly used for pretreatment or separation of biomass, and a mixture thereof. It should be appreciated that in some instances the rinse fluid can be a non-aqueous solvent or solution. Suitable organic solvents include alcohols and ketones as well as those that are well known by one skilled in the art. Suitable acids include sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid as well as other acids that are well known to on skilled in the art. Exemplary bases include sodium hydroxide, ammonium hydroxide and potassium hydroxide, as well as other bases that are well known to one skilled in the art.
In other embodiments, one or more fluids that are used in processes of the invention can be recovered and recycled using methods known to one skilled in the art. Different mixture of fluid can be introduced into different reactions zones. Each zone can utilize substantially different chemistry. For example, referring again to
The composition of the rinse fluid along a single reaction zone can be modified with the introduction of additional fluid. For example, injection of water at 19 and alkali solution at 21 (see, for example,
In this example, the second reaction zone (3) operates under pressure at temperatures up to 230° C. Water for counter-flow is fed by a high pressure piston pump (12) through a heat exchanger (13) and a heater (14). The counter-flowing water is restricted by the dynamic plugs (6) and (7) formed from the material being processed, and is discharged through the dynamic filter (15), the heat exchanger (13), and a progressing cavity pump (16) operated in reverse. This water solution is used as the wetting/washing agent in the first reaction zone (2) in order to avoid product dilution that would occur from the use of fresh water. The plugs carry some liquid between reaction zones just as any filter would. In some applications, the feedstock may be naturally wet enough that additional wetting from the pump (16) is not needed. The heat exchanger (13) serves both to cool the liquid output to prevent flashing and to recycle heat to the liquid feed for energy conservation.
The third (4) and fourth (5) reaction zones operate under pressure at temperatures up to 235° C. and illustrate a situation in which two reaction zones do not need to be separated by a dynamic plug. Fresh water for counter-flow is fed by a high pressure piston pump (17) through a heat exchanger (18) and a heater (19). This water rinses the products prior to their discharge through dynamic plug (8). A concentrated alkali solution may be fed at an appropriate rate by pump (20) through a heater (21) to mix with the counter-flowing water rinse from the fourth reaction zone (5). This mix then provides the liquid feed to the third reaction zone (4) in which base assisted or catalyzed reactions may occur (e.g., depolymerization of lignin and residual hemicellulose). This method of utilizing rinse water conserves chemicals and minimizes waste disposal problems at no additional cost for heating and pumping. In the same manner as in the second reaction zone (3), the counter-flowing solution from the third reaction zone (4) is discharged through the dynamic filter (22), the heat exchanger (18), and a progressing cavity pump (23). This alkali discharge (24) may contain alkali reaction products (e.g., depolymerized lignin and hemicellulose) as well as particulates and fines.
Particulates below particular sizes may be carried in a stream of rinse fluid and not with the larger solid particles. These small particles should be discharged with the liquid so they do not accumulate and clog the filter system. Embodiments of the present invention include a dynamic filter, which may be produced by modifying a unit called a “vacuum stuffer” that is manufactured by Entek Manufacturing. The vacuum stuffer unit includes a twin-screw extruder fabricated with close tolerances.
Two methods have been developed for the discharge of solids: If solids exiting the last dynamic plug are too dry to be managed, water may be added in a mixing zone (25) of the extruder to create a slurry. This slurry can then be injected into a progressing cavity pump operated in reverse to reduce the pressure much as with the liquid discharge previously described (23). The water added may be cold to keep the vapor pressure of the resulting slurry lower than atmospheric pressure as the slurry enters the pump.
In some applications, further disruption of the components of the feedstock may be desired. Embodiments of the present invention provide for additional disruption of the feedstock with a steam explosion. In this case, slurry water (25) is added hot (e.g., greater than 130° C.) and a component like the pressurized discharge unit shown in
As noted above, embodiments of the invention also include systems and apparatuses with two or more separate extruders that are coupled together.
In
Extruders (1) and (35) are joined in a barrel cross (39) wherein the two sets of screws overlap as illustrated in
The next motor driven extruder (36) in
This extruder (37) may differ in operation from the apparatus of
Having described several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the invention. Additionally, a number of well known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.
As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a process” includes a plurality of such processes and reference to “the electrode” includes reference to one or more electrodes and equivalents thereof known to those skilled in the art, and so forth.
Also, the words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.
It should be appreciated that any numeric value given herein includes numeric values within ±10% range. For example, pH 2 means pH ranging from pH 1.8 to pH 2.2, and the amount of theoretical lignin of 50% means the amount of theoretical lignin ranging from 45% to 55%.
This application is a continuation-in-part of U.S. patent application Ser. No. 12/782,471, filed May 10, 2010, which is a continuation of U.S. patent application Ser. No. 12/120,998, filed May 15, 2008, now U.S. Patent No. 7,717,364, issued May 10, 2010, which is a continuation of U.S. patent application Ser. No. 11/158,831, filed Jun. 21, 2005, now U.S. Pat. No. 7,600,707, issued Oct. 13, 2009, the entire disclosure of which is incorporated herein by reference in their entirety. U.S. patent application Ser. No. 11/158,831 is related to U.S. patent application Ser. No. 10/081,930, filed Feb. 20, 2002, now U.S. Pat. No. 6,620,292, issued Sep. 16, 2003, which is a continuation-in-part of U.S. patent application Ser. No. 09/640,815 filed Aug. 16, 2000, now U.S. Pat. No. 6,419,788, issued Jul. 16, 2002, the entire contents of these related patents are also incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12120998 | May 2008 | US |
| Child | 12782471 | US | |
| Parent | 11158831 | Jun 2005 | US |
| Child | 12120998 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12782471 | May 2010 | US |
| Child | 13424374 | US |
