Abstract:
A novel class of flowable biomass feedstock particles with unusually large surface areas that can be manufactured in remarkably uniform sizes using low-energy comminution techniques. The feedstock particles are roughly parallelepiped in shape and characterized by a length dimension (L) aligned substantially with the grain direction and defining a substantially uniform distance along the grain, a width dimension (W) normal to L and aligned cross grain, and a height dimension (H) normal to W and L. The particles exhibit a disrupted grain structure with prominent end and surface checks that greatly enhances their skeletal surface area as compared to their envelope surface area. The L×H dimensions define a pair of substantially parallel side surfaces characterized by substantially intact longitudinally arrayed fibers. The W×H dimensions define a pair of substantially parallel end surfaces characterized by crosscut fibers and end checking between fibers. The L×W dimensions define a pair of substantially parallel top surfaces characterized by some surface checking between longitudinally arrayed fibers. At least 80% of the particles pass through a ¼ inch screen having a 6.3 mm nominal sieve opening but are retained by a No. 10 screen having a 2 mm nominal sieve opening. The feedstock particles are manufactured from a variety of plant biomass materials including wood, crop residues, plantation grasses, hemp, bagasse, and bamboo.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
       [0001]    This application claims priority from provisional application No. 61/343,005 filed Apr. 22, 2010 and application Ser. No. 12/907,526 filed Oct. 19, 2010. 
     
    
     STATEMENT OF GOVERNMENT LICENSE RIGHTS 
       [0002]    This invention was made with government support by the Small Business Innovation Research program of the U.S. Department of Energy, Contract SC0002291. The government has certain rights in the invention. 
     
    
     FIELD OF THE INVENTION 
       [0003]    Our invention relates to manufactured particles of plant biomass useful as bioenergy feedstocks. 
       BACKGROUND OF THE INVENTION 
       [0004]    Wood particles, flakes, and chips have long been optimized as feedstocks for various industrial uses (see, e.g., U.S. Pat. Nos. 2,776,686, 4,610,928, 6,267,164, and 6,543,497), as have machines for producing such feedstocks. 
         [0005]    Optimum feedstock physical properties vary depending on the product being produced and/or the manufacturing process being fed. In the case of cellulosic ethanol production, the feedstock should be comminuted to a cross section dimension of less than 6 mm for steam or hot water pretreatment, and to less than 3 mm for enzymatic pretreatment. Uniformity of particle size is known to increase the product yield and reduce the time of pretreatment. Uniformity of particle size also affects the performance of subsequent fermentation steps. Piece length is also important for conveying, auguring, and blending. Over-length pieces may tangle or jam the machinery, or bridge together and interrupt gravity flow. Fine dust-like particles tend to fully dissolve in pretreatment processes, and the dissolved material is lost during the washing step at the end of preprocessing. 
         [0006]    Particle shape can be optimized to enhance surface area, minimize diffusion distance, and promote the rate of chemical or enzyme catalyst penetration through the biomass material. 
         [0007]    Gasification processes that convert biomass to syngas present a different set of constraints and tradeoffs with respect to optimization of particle shape, size, and uniformity. For such thermochemical conversions, spherical shapes are generally favored for homogeneous materials, and enhancement of surface area is less important. Cellulosic plant derived feedstocks are not homogeneous, and thus optimal properties involve complex tradeoffs. 
         [0008]    A common concern in producing all bioenergy feedstocks is to minimize fossil fuel consumption during comminution of plant biomass to produce the feedstock. 
       SUMMARY OF THE INVENTION 
       [0009]    Herein we describe a novel class of flowable biomass feedstock particles with unusually large surface area to volume ratios that can be manufactured in remarkably uniform sizes using low-energy comminution techniques. The feedstock particles are roughly parallelepiped in shape and characterized by: a length dimension (L) aligned substantially with the grain and defining a substantially uniform distance in the grain direction; a width dimension (W) normal to L and aligned cross grain; and a height dimension (H) normal to W and L. The particles exhibit a disrupted grain structure with prominent end and surface checks that greatly enhance their skeletal surface area as compared to their envelope surface area. Representative wood feedstock particles of the invention are shown in  FIG. 1B , which indicates how the nominal parallelepiped shape of the particles is cracked open by pronounced checking that greatly increases surface area. The L×H dimensions define a pair of substantially parallel side surfaces characterized by substantially intact fibers arrayed along the grain. The W×H dimensions define a pair of substantially parallel end surfaces characterized by crosscut fibers and end checking between fibers. The L×W dimensions define a pair of substantially parallel top surfaces characterized by some surface checking between longitudinally arrayed fibers. The feedstock particles can be manufactured from a variety of plant biomass materials including wood, crop residues, plantation grasses, hemp, bagasse, and bamboo. 
         [0010]    The feedstock particles preferably exhibit an experimental temperature compensated conductivity (CC) of greater than 8 μS as determined by the following experimental steps: measure an initial CC of 500 ml of distilled water at 25° C. in a glass vessel; add 10 g of the particles into the water; stir the particles at 250 RPM in the water at 25° C. for 30 minutes; measure the CC of the water at 30 min, and calculate the experimental CC by subtracting the initial CC from the CC at 30 minutes and thereby determine that the calculated experimental CC of the particles is greater than 8 μS. More preferably, the calculated experimental CC of the particles exhibit an experimental temperature compensated conductivity (CC) of greater than greater than 10 μS, and most preferably greater than 12 μS. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0011]      FIG. 1  is a photograph of similarly sized (A) prior art wood cubes typical of coarse sawdust or chips, and (B) wood feedstock particles of the present invention; 
           [0012]      FIG. 2  is a perspective view of a prototype rotary bypass shear machine suitable to produce plant biomass feedstock particles of the present invention; and 
           [0013]      FIG. 3  is a graph of ion conductivity leachate data from cubes and particles like shown in  FIG. 1 . 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
       [0014]    We have applied engineering design principles to develop a new class of plant biomass feedstock particles characterized by consistent piece size uniformity, high skeletal surface area, and good flow properties. The feedstock particles can be conveniently manufactured from a variety of plant biomass materials at relatively low cost using low-energy comminution processes. 
         [0015]    The term “plant biomass” as used herein refers generally to encompass all plant materials harvested or collected for use as industrial feedstocks, including woody biomass, hardwoods and softwoods, energy crops like switchgrass,  Miscanthus , and giant reed grass, hemp, bagasse, bamboo, and agricultural crop residues, particularly corn stover. 
         [0016]    The term “grain” as used herein refers generally to the arrangement and longitudinally arrayed direction of fibers within plant biomass materials. “Grain direction” is the orientation of the long axis of the dominant fibers in a piece of plant biomass material. 
         [0017]    The terms “checks” or “checking” as used herein refer to lengthwise separation and opening between plant fibers in a biomass feedstock particle. “Surface checking” may occur on the lengthwise surfaces a particle (that is, on the L×H and L×W surfaces); and “end checking” occurs on the cross-grain ends (W×H) of a particle. 
         [0018]    The term “skeletal surface area” as used herein refers to the total surface area of a biomass feedstock particle, including the surface area within open pores formed by checking between plant fibers. In contrast, “envelope surface area” refers to the surface area of a virtual envelope encompassing the outer dimensions the particle, which for discussion purposes can be roughly approximated to the particle&#39;s extent volume. Thus, the envelope surface area is equal to the skeletal surface area minus the surface area within checks and other open pores of the particle. 
         [0019]    The terms “temperature calibrated conductivity,” “calibrated conductivity,” and “CC” as used herein refer to a measurement of the conductive material in an aqueous solution adjusted to a calculated value which would have been read if the sample had been at 25° C. 
         [0020]    The term “sinking” as opposed to “floating” is used herein to characterize feedstock particles that sink in distilled water following stirring at 250 RPM for 15 minutes at 25° C. 
         [0021]    The new class of plant biomass feedstock particles described herein can be readily optimized for various conversion processes that produce bioenergy, biofuel, and bioproducts. 
         [0022]    Each particle is intended to have a specified and substantially uniform length along the grain direction, a width tangential to the growth rings (in wood) and/or normal to the grain direction, and a height (thickness in the case of veneer) radial to the growth rings and/or normal to the width and L dimensions. 
         [0023]    We have found it very convenient to use wood veneer from the rotary lathe process as a raw material. Peeled veneer from a rotary lathe naturally has a thickness that is oriented with the growth rings and can be controlled by lathe adjustments. Moreover, within the typical range of veneer thicknesses, the veneer contains very few growth rings, all of which are parallel to or at very shallow angle to the top and bottom surfaces of the sheet. In our application, we specify the veneer thickness to match the desired wood particle height (H) to the specifications for a particular conversion process. 
         [0024]    The veneer may be processed into particles directly from a veneer lathe, or from stacks of veneer sheets produced by a veneer lathe. Plant biomass materials too small in diameter or otherwise not suitable for the rotary veneer process can be sliced to pre-selected thickness by conventional processes. Our preferred manufacturing method is to feed the veneer sheet or sliced materials into a rotary bypass shear with the grain direction oriented across and preferably at a right angle to the machine&#39;s processing head. 
         [0025]    The rotary bypass shear that we designed for manufacture of wood feedstock particles is a shown in  FIG. 2 . This prototype machine  10  is much like a paper shredder and includes parallel shafts  12 ,  14 , each of which contains a plurality of cutting disks  16 ,  18 . The disks  16 ,  18  on each shaft  12 ,  14  are separated by smaller diameter spacers (not shown) that are the same width or greater by 0.1 mm thick than the cutting disks  16 ,  18 . The cutting disks  16 ,  18  may be smooth  18 , knurled (not shown), and/or toothed  16  to improve the feeding of veneer sheets  20  through the processing head  22 . Each upper cutting disk  16  in our rotary bypass shear  10  contains five equally spaced teeth  24  that extend 6 mm above the cutting surface  26 . The spacing of the two parallel shafts  12 ,  14  is slightly less than the diameter of the cutting disks  16 ,  18  to create a shearing interface. In our machine  10 , the cutting disks  16 ,  18  are approximately 105 mm diameter and the shearing overlap is approximately 3 mm. 
         [0026]    This rotary bypass shear machine  10  used for demonstration of the manufacturing process operates at an infeed speed of one meter per second (200 feet per minute). The feed rate has been demonstrated to produce similar particles at infeed speeds up to 2.5 meters per second (500 feet per minute). 
         [0027]    The width of the cutting disks  16 ,  18  establishes the length of particles produced since the veneer  20  is sheared at each edge  28  of the cutters  16 ,  18  and the veneer  20  is oriented with the fiber grain direction across the cutter disks  16 ,  18  parallel to the cutter shafts  12 ,  14 . Thus, wood particles from our process are of much more uniform length than are particles from shredders, hammer mills and grinders which have a broad range of random lengths. The desired and predetermined length of particles is set into the rotary bypass shear machine  10  by either installing cutters  16 ,  18  having widths equal to the desired output particle length or by stacking assorted thinner cutting disks  16 ,  18  to the appropriate cumulative cutter width. 
         [0028]    Fixed clearing plates  30  ride on the rotating spacer disks to ensure that any particles that are trapped between the cutting disks  16 ,  18  are dislodged and ejected from the processing head  20 . 
         [0029]    We have found that the wood particles leaving the rotary bypass shear machine  10  are broken (or crumbled) into short widths due to induced internal tensile stress failures that are typically aligned with winter- and summer-wood rings. Thus the resulting particles are of generally uniform length along the wood grain, and of a uniform thickness (when made from veneer), but vary somewhat in width principally associated with the microstructure and natural growth properties of the raw material species. Most importantly, frictional and Poisson forces that develop as the biomass material  20  is sheared across the grain at the cutter edges  28  tend to create end checking that greatly increases the skeletal surface areas of the particles. 
         [0030]    The output of the rotary bypass shear  10  may be used as is for some conversion processes such as densified briquette manufacture, gasification, or thermochemical conversion. However, many end-uses will benefit if the particles are screened into narrow size fractions that are optimal for the end-use conversion process. In that case, an appropriate stack of vibratory screens or a tubular trommel screen with progressive openings can be used to remove those particles that are larger or smaller than desired. 
         [0031]    In the event that the feedstock particles are to be stored for an extended period or are to be fed into a conversion process that requires very dry feedstock, the particles may be dried prior to storage, packing or delivery to an end user. 
         [0032]    To date we have used this prototype machine  10  to make feedstock particles in 3/16″ and ¾″ lengths from a variety of plant biomass materials, including: peeled softwood and hardwood veneers ( 1/10″ and ⅙″); sawed softwood and hardwood veneers; crushed softwood and hardwood branches and limbs; hog fuel; corn stover; switchgrass; and bamboo. The L×W surfaces of peeled veneer particles appear to retain the tight-side and loose-side characteristics of the raw material. Crushed wood and fibrous biomass mats are also suitable starting materials, provided that all such biomass materials are aligned across the cutters  16 ,  18  substantially parallel to the grain direction, and preferably within 10° and at least within 30° parallel to the grain direction. 
         [0033]    We currently consider the following size ranges as particularly useful biomass feedstocks: (1) H should not exceed a maximum from 1 to 16 mm, in which case W is between 1 mm and 1.5× the maximum H, and L is between 0.5 and 20× the maximum H; or (2) preferably, L is between 4 and 70 mm, and each of W and L is equal to or less than L. More preferably, for flowability and high surface area to volume ratios, the L, W, and H dimensions are selected so that at least 80% of the particles pass through a ¼ inch screen having a 6.3 mm nominal sieve opening but are retained by a No. 10 screen having a 2 mm nominal sieve opening. Most preferably, for uniformity as reaction substrates, at least 90% of the particles should pass through either: (1) a ¼″ screen having a 6.3 mm nominal sieve opening but are retained by a No. 4 screen having a 4.75 mm nominal sieve opening; or (2) a No. 4 screen having a 4.75 mm nominal sieve opening but are retained by a No. 8 screen having a 2.36 mm nominal sieve opening; or (3) a No. 8 screen having a 2.36 mm nominal sieve opening but are retained by a No. 10 screen having a 2 mm nominal sieve opening. 
         [0034]    Surprisingly significant percentages of the above most-preferably sized wood particles readily sink in water, and this presents the prospect of selectively sorting lignin-enriched particles (by gravity and/or density) and more economical preprocessing. 
         [0035]    The following laboratory experiments demonstrate these and other unusual and commercially valuable properties of this new class of biomass feedstock particles. 
       EXAMPLES 
     Ion Conductivity Leachate Experiments 
       [0036]    Buckmaster recently evaluated electrolytic ion leakage as a method to assess activity access for subsequent biological or chemical processing of forage or biomass. (Buckmaster, D. R., Assessing Activity Access of forage or biomass, Transactions of the ASABE, 51(6):1879-1884, 2008.) He concluded that ion conductivity of biomass leachate in aqueous solution was directly correlated with activity access to plant nutrients within the biomass materials for subsequent biological, chemical, or even combustion processes. 
         [0037]    In the following experiments, we compared leachate rates from various types of wood feedstocks. 
         [0038]    Materials 
         [0039]    Wood particles of the present invention were manufactured as described in above described machine  10  using 3/16″ wide cutters from a knot-free sheet of Douglas fir ⅙″ thick veneer (10-15% moisture content). The resulting feedstock was size screened, and a 10 g experimental sample was collected of particles that in all dimensions passed through a ¼″ screen (nominal sieve opening 6.3 mm) but were retained by a No. 4 screen (nominal sieve opening 4.75 mm). Representative particles from this experimental sample (FS-1) are shown in  FIG. 1B . 
         [0040]    Similarly sized cubes indicative of the prior art were cut from the same veneer sheet, using a Vaughn® Mini Bear Saw™ Model BS 150D handsaw. The sheet was cut cross-grain into approximately 3/16″ strips. Then each strip was gently flexed by finger pressure to break off roughly cube-shaped particles of random widths. The resulting feedstock was size screened, and a 10 g control sample was collected of particles that in all dimensions passed through the ¼″ screen but were retained by the No. 4 screen. Representative cubes from this control sample (Cubes-1) are shown in  FIG. 1A . 
         [0041]    The outer (extent) length, width, and height dimensions of each particle in each sample were individually measured with a digital caliper and documented in table form. Table 1 summarizes the resulting data. 
         [0000]    
       
         
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Number of 
                   
                   
                   
               
               
                 Samples (10 g) 
                 pieces 
                 Length (L) 
                 Width (W) 
                 Height (H) 
               
               
                   
               
             
             
               
                 Control cubes 
                 n = 189 
                 Mean 5.5 
                 Mean 5.0 
                 Mean 3.9 
               
               
                 (Cubes-1) 
                   
                 SD 0.48 
                 SD 1.17 
                 SD 0.55 
               
               
                 Experimental particles 
                 n = 292 
                 Mean 5.3 
                 Mean 5.8 
                 Mean 3.3 
               
               
                 (FS-1) 
                   
                 SD 0.74 
                 SD 1.23 
                 SD 0.82 
               
               
                   
               
             
          
         
       
     
         [0042]    The Table 1 data indicates that the extent volumes of these size-screened samples were not substantially different. Accordingly, the cubes and particles had roughly similar envelope surface areas. Yet the 10 gram experimental sample contained 54% (292/189) more pieces than the 10 gram control sample, which equates to a mean density of 0.34 g/particle (10/292) as compared to 0.053 g/cube.  FIG. 1  indicates that the roughly parallelepiped extent volumes of typical particles ( 1 B) contain noticeably more checks and air spaces than typical cubes ( 1 A). These differences demonstrate that the feedstock particles of the invention had significantly greater skeletal surface areas than the control cubes indicative of prior art coarse sawdust and chips. One would thus expect the particles to exhibit more ion leachate than the cubes in aqueous solution. 
         [0043]    Individual handling during the caliper measurements tended to beat up the Table 1 particles (FS-1), and so a second set of 10 g samples of cubes (Cubes-2) and particles (FS-2) were made as described above from another sheet of veneer for ion conductivity leachate assessments as described below. 
       Equipment 
       [0044]    Jenco® Model 3173/3173R Conductivity/Salinity/TDS/Temperature Meter 
         [0045]    Corning® Model PC-420 Laboratory Stirrer/Hot Plate 
         [0046]    Aculab® Model VI-1200 Balance 
       Methods 
       [0047]    Ion conductivity of biomass leachate in aqueous solution was assessed for each of the samples by the following protocol: 
         [0048]    (1) Measure the initial temperature compensated conductivity (CC, in microSiemens (μS)) of 500 ml of distilled water maintained at ˜25° C. in a glass vessel. 
         [0049]    (2) Add a 10 g sample of feedstock pieces into the water, and stir the pieces at 250 RPM in the water at ˜25° C. for 60 minutes. 
         [0050]    (3) Briefly stop stirring and measure the CC of the water at 15-minute intervals; and note if any of the pieces sink to the bottom of the vessel during these brief non-stirring intervals. 
         [0051]    (4) Calculate an experimental CC value for comparison purposes by subtracting the initial CC from the CC at 30 minutes. 
       Results 
       [0052]    The resulting CC data is shown in Table 2 and plotted  FIG. 3 . 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                   
                 Temperature Calibrated Conductivity (μS) 
               
             
          
           
               
                 Sample 
                 0 min 
                 15 min 
                 30 min 
                 45 min 
                 60 min 
               
               
                   
               
             
          
           
               
                 Control cubes 
                 1.9 
                 6.7 
                 8.6 
                 9.8 
                 10.8 
               
               
                 (Cubes-2) 
                   
                   
                   
                   
                   
               
               
                 Experimental particles 
                 1.9 
                 12.0 
                 15.0 
                 16.5 
                 17.8 
               
               
                 (FS-2) 
               
               
                   
               
             
          
         
       
     
         [0053]    These results indicate that the particles exhibited nearly twice the activity index of similarly sized cubes that generally lacked the cross-grain end checking that characterizes the biomass feedstocks of the invention. 
         [0054]    In addition, all of the cubes were observed to consistently float throughout the 60 min soak and swirl period. In contrast, a noticeable proportion of the experimental particles sank when the stir bar was turned off during the CC measurements. 
         [0055]    These results are consistent with our other experimental observations to date, as summarized in the following Table 3. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Sample 
                 Temperature Calibrated Conductivity (μS) 
                   
               
             
          
           
               
                 Size 
                 # 
                 0 min 
                 15 min 
                 30 min 
                 45 min 
                 60 min 
                 Float % 
                 Sink % 
               
               
                   
               
             
          
           
               
                 Pass 1/4″ screen &amp; 
                 009/4a 
                 1.9 
                 9.6 
                 11.8 
                   
                   
                   
                   
               
               
                 retained by #4 screen 
                 009/4b 
                 2.0 
                 10.7 
                 13.1 
               
               
                   
                 0124h 
                 2.0 
                 7.6 
                 9.1 
                 9.9 
                   
                 84 
                 16 
               
               
                   
                 012/4m 
                 1.8 
                 6.3 
                 7.6 
                 8.5 
                   
                 87.5 
                 12.5 
               
               
                   
                 014/4Cr 
                 2.0 
                 8.0 
                 9.7 
                 10.6 
                   
                 71 
                 29 
               
               
                   
                 016/4sp 
                 2.3 
                 6.8 
                 8.2 
                 9.0 
                   
                 92 
                 8 
               
               
                   
                 Cubes-1 
                 2.3 
                 4.8 
                 5.8 
                 6.4 
                   
                 100 
                 0 
               
               
                   
                 Cubes-2 
                 1.9 
                 6.7 
                 8.6 
                 9.8 
                 10.8 
                 100 
                 0 
               
               
                   
                 FS-2 
                 1.9 
                 12.0 
                 15.0 
                 16.5 
                 17.8 
               
               
                 Pass No. 4, 
                 009/8a 
                 1.9 
                 10.9 
                 13.2 
                 14.5 
                 15.7 
               
               
                 No. 8 retain 
                 009/8b 
                 2.0 
                 11.5 
                 14.1 
                 15.7 
                 16.6 
               
               
                   
                 012/8h 
                 1.8 
                 7.1 
                 8.5 
                 9.4 
                   
                 73 
                 27 
               
               
                   
                 012/8m 
                 2.0 
                 7.6 
                 9.1 
                 9.9 
                   
                 77 
                 23 
               
               
                   
                 014/Cr 
                 2.3 
                 10.3 
                 12.6 
                 13.9 
                   
                 51 
                 49 
               
               
                 No. 8/ 
                 012/10h 
                 1.9 
                 9.5 
                 11.2 
                 12.1 
                   
                 52 
                 48 
               
               
                 No. 10 
                 012/10m 
                 1.9 
                 9.2 
                 11.0 
                 11.8 
                   
                 52 
                 48 
               
               
                   
               
             
          
         
       
     
         [0056]    Referring to Table 3, the #009 samples were made from 1/10″ Douglas fir veneer, and the other particle samples which were made from ⅙″ Douglas fir veneer, as were the Cubes-1 and Cubes-2 samples. 
         [0057]    While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.