CA2655111C - Fibrous materials and compositions - Google Patents

Abstract

This invention relates to the fibrous mate.pi.als, methods of making fibrous materials, compositions that include fibrous materials and a resin, or compositions that included the fibrous materials and bacteria and/or enzymes In addition, the use of the fibrous materials compositions are disclosed. For example, the fibrous materials can be operated on by a microorganism to produce a fuel compnsing hydrogen, an alcohol such as ethanol, an organic acid and/or hydrocarbon

Description

FIBROUS MATERIALS AND COMPOSITIONS
TECHNICAL FIELD

This invention relates to fibrous materials and to compositions.
BACKGROUND
Fibrous materials, e.g., cellulosic and lignocellulosic materials, are produced, processed, and used in large quantities in a number of applications.
Often such fibrous materials are used once, and then discarded as waste.

Various fibrous materials, their uses and applications have been described in U.S. Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105.

SUMMARY
Generally, this invention relates to fibrous materials, methods of making fibrous materials, compositions that include fibrous materials (e.g., composites that include the fibrous materials and a resin, or compositions that include the fibrous materials and bacteria and/or an enzyme), and to uses of the same. For example, the compositions can be used to make ethanol, or a by-product, such as a protein or lignin, or applied to a structure as insulation.

Any of the fibrous materials disclosed herein can be used in combination with any of the fibrous materials, resins, additives, or other components disclosed in U.S. Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105. In turn, these fibrous materials and/or components can be used in any of the applications, products, procedures, et cetera disclosed in any of these patents or in this application.

The fibrous materials or compositions that include the fibrous materials can be, e.g., associated with, blended with, adjacent to, surrounded by, or within a structure or carrier (e.g., a netting, a membrane, a flotation device, a bag, a shell, or a biodegradable substance). Optionally, the structure or carrier may itself be made from a fibrous material, or of a composition that includes a fibrous material.
In some embodiments, the fibrous material is combined with a material, such as a protic acid, that enhances the rate of biodegradation of the fibrous material. In some embodiments, the fibrous material is combined with a material that retards degradation of the fibrous material, such as a buffer.

The ratio of fibrous materials to the other components of the compositions will depend upon the nature of the components, and can be readily adjusted for a specific product application.

Any of the fibrous materials described herein, including any of the fibrous materials made by any of the methods described herein, can be used, e.g., to form composites with resin, or can be combined with bacteria and/or one or more enzymes to produce a valuable product, such as a fuel (e.g., ethanol, a hydrocarbon, or hydrogen).

In one aspect, the invention features methods of making fibrous materials.
The methods include shearing a fiber source to provide a first fibrous material, and passing the first fibrous material through a first screen having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material. The fiber source can, e.g., be cut into pieces or strips of confetti-like material prior to the shearing.

According to one aspect of the present invention, there is provided a method of making a fuel, the method comprising: shearing a fiber source that is a cellulosic or lignocellulosic material to provide a first fibrous material;
passing the first fibrous material through a first screen having an average opening size of about 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material; and combining the second fibrous material with a bacterium and/or enzyme, the bacterium and/or enzyme utilizing the second fibrous material to produce a fuel comprising hydrogen, an alcohol, an organic acid and/or a hydrocarbon; wherein the second fibrous material has a

2 BET (Brunauer, Emmet and Teller) surface area of greater than about 0.25 m2/g and a porosity of greater than 25%.

According to another aspect of the present invention, there is provided a method of making a fuel, the method comprising: shearing a fiber source that is a cellulosic or lignocellulosic material to provide a first fibrous material; passing the first fibrous material through a first screen having an average opening size of about 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material having a BET
(Brunauer, Emmet and Teller) surface area of greater than about 0.25 m2/g and a porosity of greater than 25%; hydrolyzing the second fibrous material to provide a hydrolyzed material; and combining the hydrolyzed material with bacterium and/or enzyme, the bacterium and/or enzyme utilizing the hydrolyzed material to produce a fuel comprising hydrogen, an alcohol, an organic acid and/or a hydrocarbon.

In some embodiments, the average opening size of the first screen is less than 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.20 mm (1/128 inch, 0.0078125 inch), or even less than 0.10 mm (1/256 inch, 0.00390625 inch).

In specific implementations, the shearing is performed with a rotary knife cutter. If desired, the shearing can be performed while the fiber source is dry (e.g., having less than 0.25 percent by weight absorbed water), hydrated, or even while the fiber source is partially or fully submerged in a liquid, such as water or isopropanol.

The second fibrous material can, e.g., be collected in a bin having a pressure below nominal atmospheric pressure, e.g., at least 10 percent below nominal atmospheric pressure, at least 50 percent below nominal atmospheric pressure, or at least 75 percent below nominal atmospheric pressure.

The second fibrous material can, e.g., be sheared once or numerous times, e.g., twice, thrice, or even more, e.g., ten times. Shearing can "open up"
and/or "stress" the fibrous materials, making the materials more dispersible, e.g., in a solution or in a resin.

2a The second fibrous material can be, e.g._ sheared and the Ic=511:.#3? j fibrous material passed tarea h g the >a tsi'si .a.

3C. sec nd ti broius material can be sheared, and the u i ng fibrous i aterial passed -trough i. second screen haying an average opening Sze less than first providing 6 a third Brous 1 ateria^:.

A rat# 5 of c aver ge length-to-diameter a io of the second à hrous mat Vial to an average ,L #? ??-~i3r4 T 3. t. rdt.so of the third fibrous mate .i El can be, u-.g ., less than 1 .5, es thha n 1.4, less than 115, or even less than LL
.

~.l D \.,f < ~e a ga;
T 'he b~\,..{3:iC~ fibrous taiii be, ~..-~.y ~?ai55 a`ia~E~,1': a SrC~.d screen :, ha<iti. _`r an OM-1,11-rage 0 opening size 'Was than the first screen.

2 `,e shearing and passing can be, Q.&, performed wncunrcnaly.

The second fibrous material can have an average le .1:^Eo-diaifinete. ratio ol"
'. f L # t=# ttlhav greater than 251i:I, or even greater than 50/..

Fos example, an average length of the Second fibrous mate #al C`sEn be e w``e n 50..5 15 mm and 2,45 mm, e.g., between 0.75 mm and 1,0 is?m, For ex iampl , an iv e atge 'Ei iadt of the C?.nd fibrous mater al can be between 5 l.tm and 5031 `.m. e.g., betweel-i 10 ti..m ai#, 30 m.

t ..dard1 deviation of a. length of the second fibrous material c n be Jess than 60 A standard, ~.p<s. \ i ge i g the N~ ju,.t t 3 a n ,LY:a$t of all average ~Il~,t~l~a~ , t33 C. second fibrous z.li..~#ea.F,e.g., ~less tht1:E~. O k =..+
peEt...,#atof"A:a~a 20 to so-me=bodimQuts, a BET suwface area of tile second fibrous matenal is greater than n00 ni +g eg., gueater thaii. 1.0 ni Va'3. greater than 1.5 rn. g, greater than 1,75 m tom;, 0 x 2/ Ã , greater than 25.0 rr, 'gF eat.. t :1_iIE ).f t i' fps, greater than ~ .5 m g, greater t' an ': :.

or even C>ff e ter= than 100.0 In the ,,E 'i q some eodiMi nits, a porosity of rE sceond fibrous iniaLerial is groi'e'r than 25 u c eeiii,, greater than 50 percent greater tF~iiii# 75 percent, greater than 85 per e#:'s, greater than 90 percent, greater t an 92 percent, 'enter than 95 percent, or even greater than })9 ner>ent.

#i t~.t t :%\',Il , i i{Ã +.1> t:ntent .
in sped fie embod nie"nts the screen is formed by The fiber source can include, e.g., a cellulosic iliateri al, a ligii.oeciluao ale materia' .

Iii sd?.m eo ida tints, the fiber source Includes Ei. blend of .,# 5; e.g,, fibers derived ?E

from is paper source and fibers derived from. a textile source, cotton.

In another aspect. the invention f atures methods of inakilig that i , Y, ~ j _ x "t include S 7t ai.?.s ?:?d F source `. 3 pre i ti, a #: J*. fibrous .i EEtC
iaa, and passing t ho fibrous 4%

9f71ar ,.i . i l through a first scree . to provide a second fibrous material.
A ratio of an average engt i'to t iiifa et r ratio of the first fibrous la.W`r'lfl to 5 1 : rt average iGf. `g .j= Z f tae ~ nat}:-tot,= t second fihr o,as ,r aterial rs less than I .?.

in another asneL O he invention feawres methods of makir fibrous f:t ice fix?
that u ilnclud. shearing a fiber source to provide a first fibrous slate pit.;
passing the ; l.slrc t.s material through a fast screen t i provide a second fibrous, inateria`, and then. shearing the :ecz# tf fibrous material again to provide a 1-iirtf fibrous lateÃia.l.

in another aspect, the invention . z. J.T w composites tar Compositions made fto,am any of the fibrous ? \#a.tteri als described erein. exam pie, comp sition can include xil? S' .;ill{
fibrous mmatirri; is d sccri ed herein and a bacterium < lc .'c? an enr=y ~i3e. The compositions that include any of the fibrous mate1iais described herein and dhe bclk.,. :
ulA, iI( of enzyme can be in. dry state, or they can include a liquid, such as water.

For e`a nple, the composite can be in the : of'.m of a stepping stool, -pipes, panels, decking mater: rls, board"", housings, sheets, blocks, bricks, poles, fencing I .C 1a#~i~ i. doors, 15, shutters, awwnings shades,s:igiis, f anics, window casings, backboards flooring, tiles, railroad ties, tw s, tool handles, stalls, films, wrap:,, tapes, boxes, cask ets, racks, casings, )inders, dividers, ails, m,_:ts, ar: mes, bookcases, ul cures i hairs, table s, desks, to ' , ivc, me , pa lets b.'.lr.iarl `, piers, oats, masts, septic tank, c^. l.t+_31^.11zt1 panels. computer sousing trove- and below g':"1 and electrical casings, fu rniture., picnic tables, bench s 20 shelters , r i'4 s, nang r` s Qrv rs, caskets, book covers, canes and crutches.

In another aspect, the in =entior features fibrous materials h-haA:1,Ig an average lcm -to diameter ratio of greater than 5, and having a standard deviation of _t fiber en"th of less t ran s xty percent of an average fiber length.
For e:xanxple, the average length-to-diameter ratio an be. gr'ea'ter than 30 C. o., 2\3 greater than 1 5 , greater than 25;1, greater than 35"1, greater than 45/1, or e eft 1 _ .
than 5t'/1.

For e ample, the i w~ erase lei gt:( can he between 0.5 mm õ nd 2.5 mn , ? 5 `S thes > features y: \ eilat,t making ~ 'i~'1.t5 it>.at?.,irt11` that In .s:s{`=:.
i" aspect, =t, the invention invention i,h`s t,3 " .:3 include ~ti~ caf g a fiber source to provide a first: fibrous i13 <at( pal collecting the first fibrous 3f nuteriaz and then shearing the first fibrous to 3 t?i # C '.?fad fibrous material.

in another aspect, the invention feature:," methods of .iii aking a useful i.wnal, such as c, f # f' e methods include she 3 in g a fiber so ruce ' to provide a first a# :3 ous ri 2aterial;
passirig the fir :1 fibrous nuiter'ia through a first screen having an average opening size of about 1.59 i 1#, or less (1/16 inch, 0.0625 incI to provide a second fibrous material: and owribining the second fibrous material wit ."a a bacterium and/or enzyme, the bacterium tiaii+.. L:# Cl -,n. . tili:Izfly; the second tibrotis a a`ivt.erial to producer a fuel that includes vdi oaa il, an alcohol, an organic acid and.'orr a hydro .g.;bon, The alcohol can be., e.g:, nethanol, ethanol, propano tio# #opwiol.bufa#1ol, ethyle,n e glycol, ps ?A?Yi ?e Est y (? ; 4-butane (ho", Ã ycein, or f l# fl't i of .fie i=E Z3 ?; , the Organic car, be, C'9" malofeic acid, succinic acid, giutaric acid, oleic C. id lfnoloic icid.
l v_?iic acid, lactic acit . y-a ydroxyhuty is acid, or mixtures of these a ciids, an the I: dme irhui can be, 'met bane, ethane, ropa?ie, isobutene, pone afnc, ll he.kalle, or 0 fe' isfii'e s o these lis droc;a#'1' o s, ~r#>. to wlllbinftln z With the bacterium ancti or enzyme, any of the fibrous zi'=ate3ial described herein can be hydrolyzed to break down hi iher molecular weight carbohydrates into lower molecular wei`-Slit carbohydrates.

?.n at:? l'ier aspect, t ho inventtion. features Triethods of Timak.in a use . ll material. , uch i as a fuel, by shewin a Ober source or a fibrous -material, and then combining it with a bacterium and e?, an enzyme. For example, the fiber source can be sheared ti-Ice to pro? : a1e a fibrous ,l ate i w id then the fibrous '#l at =i ial Carl 130 C:'9i'31:
;tips ` Wall a bnmerilln, "Ind"

an ;i,iothe aspect, the #.i~t 1.,f.ion rcatures ix?et ods ofdenslf ian fibrous c' p1'5x1 iz, ? `;i. The :i `ethods i clude she ariiig a fiber source to provide a i%~ srz ~.w '..os"a f `S material, co a*i.ning tx e fibii i.ts rn,,,terial with a bacterium and or enzyme to provide ii.;,-Aerial cc-f.rio?SifioTa t Tavzi lsula ii:tf? the composition in a s ibstan ially gas impermeable 111'11.c..aal and removing entrapped gas; from the eiicapsulatecs composition to dens$ '4' the composiaiwl a or exaniple,, the gas iMPO Ãimieablematerial can be in the tbrm of a ~3ce4 , and 21 the composition can be tie al '#ili'f by e.=vacuatia'ig air from the bag, and then sealing the hag.
In another aspect, the i vention features con-riposites that include a fibrous T:? aterial, a r sis` i and a For '.;-il A?là 4 the fibrous material can have an aver ge engtllwlE}^allci.i#aete ratio of g eater than 5, and a standard deviation of a fiber length of less than sixty percent of an average fiber length, i n son-le kill?, odilnents, the composite additionally 1neri.idcs a plgiilent.
the In solm implemale.i tat3ons, thdye soaked into or ,zkz accd on the.
fibers.

in another aspect, the invention features methods ofmaking com >sites that `=, ,czdde dyeing a ffibi'4>as #iate#laiti 3 t._ One fibrous material with a resin; and t1r3i.C?:g{ a co ipoJite from the v: 1~ 22~Si.fC11.X^,~~ .r .{1.? anoll1'` asp ct,, the invention. :at 3res methods of waking cornG'osite that inc. id0 Ãf~ x%3.Ã'#. :i i tii to .a resi Gel ro id ¾? i. e/reS#13 Ci?#li #:Ã1 motion f +3#?'13I.tiÃng th s{ %t' i?k3.
combination ' 3 ith a fibrous materird; and ttbianing a composite f.' .in the dy 4ex3:
c#,~,,-n inatku- ari fibrous mate.ia .

.she tt nx~ piss?lour niaterÃa ', as used herein; is a material at ?Y `:,hides numà E' E h loose, >t4 rete and separable fibers. F# Ã` example a fibrous can be prepared from a poi coated. piper or a bleached Kraft paper fiber source by si#eari 'i T .g., "vi th a rotsia'v kajfe Cutter, F he term ,screen", as used herein me ins a ill :i'Ii% er capable of sisvviingmateri o i L= 3?ilit to siz ti.g, a perforated pate, cylinder or t'i:e like, or a wire I:?'i+."'h or i z.'s i i Fl .t .
?r# #l #: l ;iii'#ats and/oz aspects can have any one of, or combà at ons ulf, . the following 15 idvan ages, The .fib o s materials are opened up i nd.') stressed, making the fileate ici?4 lilor'e dis crsib~ie, e.g., in a s lut#on or in a resit?, and making them more ~l? i pt_ le to ch amen .
enzymatic o,,- biological og'icai attack. Th : fibrous à aterials can h e. e.
L itively n= now ~'i1s' i:t' iaiii t:'si _Et igt o Ca31:1 ete ratios distribution, such that ti,e.ir propernos are cons st av-, defined, For example when. blended w th a i iolten resin or a so ton, the filet's of the ! 3 fibrous ?c.te i:als can ?_? % :y f he rheoi y of the molten resin. or solution in a consistent and r ti?L.able marine ,, e.g . resulting in rosin/fibrous, mat.eriaal combinations Inn are, e.g., Lan a:
t mold and xtziii For example, t1 he is?i'Ã u II3:liÃ.Ã':Ãiii can, silt' pass openings or channels, such as those }i. urid in or associated to i t. Ãi]_ Lctioi, Ã eld %, e.-'- "?ate s 2? hot :C:#.i?tl e0 \ +K good Cr .;S. c#.iS Molded i?'t.IS3 ~?,iL?~"ir i.bl"i !ti ?I:.9t4=l"~a1i4 G.b>~
G~~`~ii, , g~;3C?~x satc?ct,. ii iish;
15 e. f wi i. few visible speckles o a rgfi pai i G4 iF d/o r1 g g-I(n.'rate , particles, a All publications. patent applications, patents, and other inentioned herein tli'.. by t's..fC;i'Li1tE.. ln t';?<.#: Ln%lte14' fE?I alla "G_?.cit :h:.y i:=lK_:iÃili.

% tie a# c.ta?#i s and advantages of the Invention will. be apparent from -lt fs?IlC ing C
detailei i. +. scriptio_i,,, and from the claims..

so DEiSS_ R;<. DRklN-VINCS

Fig. I i:^ block diagram illustrating Conversion ofa fiber Source into, a first and second fibrous inalerial.

S

E its is a ,,,ross sectiona: vie v of a r-otarykni c cutter, igs 8 are top views of a variety of screens made tom monofilaments, Fig. `S is block diagram illustrating conversion cs a fiber source into a first, second and third fibrous r -aaterial.

th of Figs. . PA and 1013 air;.phot~, o trap,hs of fiber sources, s'. F. i tYt,, I
,A t3e,ai7~ at f a :,hotogzap.of a poi y co, tZ+x F paper container, :iriL: to lT at id Fig, L := ~ Kraft I PB
being a phIto Yr ph of i.Ãablcachid paper .. ~ p~:aer-r lI .

1 am d y 11, are re~:ea ro g fibrous ~a. al p od.-~.=..d7 e ~ i t; +. 5 ~.. ~,.aa~~.ai~ C:Etr e,:~ i3~i~"i#~E.~~~ of a ? material it s: p I'f.i po`il' co ted paper at 25 X magna ica.tioà and 1000 X magnification.
respectively. T no.
x`ibrous >matv:r iaa was produced on a rotary knife cutter on wt . _ a screen Wit:_ Figs. 13 and ? 4 are scan ning electron niicographs of a fibrous material 'proiai.ce:
_ rom bleached raft bo rdit paper at 25.1 T rwgni.f cation and 1000.

respect v ea r. The fibrous material was produced on a rotary knife cutter u6 11 sCrcel "I
s Figs. 15 and 16 are scanning electron. micrographs 'of a fibrous naatorial produced from bleached raft board paper at 25 X magnification : nd 1000 X
magnification, respectively 'The fibrous maateria was twice sheared on a rotary knife cutler Unlizinga screen wAh x 6 `x 't openings during each 1 ii777f4?.

.'i and arc ca:~nin electron micro a, ., of a i ro Ã.:it3te a3 .bier+ Lac u from bleach s aft board paper at 25 X. mxagii.rlication and e 000 X m 1,gi.fc lt:.imi, resit :;T? el v'. T' ,C fibrous material r~ ias thrice sheared on rot ry kite cutter. During the x tF t shear iili. a 1 /8 .inch screen was used, din- the second sheanna, a 1 /16 inch screen.
was Used, inn ,,uT"i.nr, the third sheai'n~ a 1/32 inch screen ,'as used.

2 5 g ice;, i`. is a block C i`agranl illustra.tin4g reveabble bulk E
ensificat oÃ'i of a fibrous mater'i.al composition, DETAILED DESCRip,riON

Referring to Fig. 1,a fiber source 10 is shearer e.g.. in a rotary kni e.
cutter, to provide a firsti ~.~?'x ?ii .mattiii a'7. first fibrous material 12 is passed through a i:st.
screen 16 having an average opening size of 1. .59 mm o less (1..l 6 aich., 0.0625 inch) i o 3s{3vide a second fibrous 1 ic:rer$cil 14. If dCs.i'4L.1, fiber sE,iii'.e 10 t`.<a:i? be stir. prior to the shearing, e.&, With a shredder. For example, when a paper is used as ,he fiber Z}..irce 1 0, the pa per cam, into r are, e e Y iz i' e ttttt i'., i a az can be first cut i:iÃtC. strips that a e,&, 1/4- to f .+õ. i tn -c wide, using, r s4area .

C g.< a counter-rotating screw shredder, such as those ià inuf.ictured t `
Munson (Utica MY), As an alternative à o shreddin , the paper can be reduced in size by cu ing to C esir d si ,i-ts3?i a ifills tine d tÃÃt I Fort example.. the guillotine cutter can be used to cut i+. à e paper into sheets that are, e.~:, I %) inches wide by 12 : .4hes loi'~..s its some embodmients, the shearing of fiber source 10 and the pass i g o the resu ting first fibrous ma %rial 12 t ..rough first screen 16 are performed cori urrer ly. The s13 111M, and tae passi `iÃg can also be performed in a b3.tch-typc process.

or e ample a ,r oturv i it tw` cutter can be us ed to con urge It {shear the fiber ,`tlzir :E
#l 0 and screen the first fibrous material 12. .Ren't'ing to Fig. a rotary knife. Cutter 20 includes a hopper 22 that can be loaded with a shreddQd fiber source 10=
prepared by shedding fiber source. 10. Shred=ded fiber source 10' is sheared .,eÃwcen station ir4 ales 24 and rotating blades 26 to provide a first fibrous material .l First fibrous t a eri zl. 12 Passe' through screen 16 having the dimensions described above, and the resuhi~tf ~5 6 i?a3C2 b ous material , is c pÃu:red in bin 30. To aid in the collection Eat t..
;second fibrous .m erial 14, bin 30 can have a. pressure blow nominal at , pheric pressure, e.g leas t l0 percent velow nominal atmospheric pressure, e.g., at least 25 :Terce.nt below nominal m{} lets,., atmospheric 1essur at least ISO percent below it ll:ii l = _ ~ ~''ia z atmospheric Press-LIT-Q, r at .~ s .
..
7 \ `:t,.~ \ i,:Y Y. T'.1 iat~i'1{}:i~Sl7t:Ã' Yis`v pressure. r~`~ stii, arz[=', In s~.aiilfi. i.tis3Eft~ > Si t:oat=s 4 Int.~~., Z'a4 ! itiai~lt S~;}iirG:L 1 . :}+F
ia~,.i,.G=Ã.`:i aa = .8 r:~ii.iatà ..

0 (Fig, 2) is utilized to maintain the bin below nominal atnno;sphe pre s it'd Shearing can be advantageous for "opening rup and "stressing"' the fibrous materials, making t .e materials more dis.pet sible, ez.g.,, in a solution or in a resip., and making them more s sceptible to chemical,enz:5'matic or biologicid attack. Without ;taishin? to b :
bound by any particular theoryit is believed, at least in some embodiments, that shearing 6 can t nctionalize fiber surfaces with functional groups, -mcill as hydroxyl or carboxylic acid g`rou s, w ii "3 can, help dispense T rs iia m y m r ` `: x ) tic " y s . i w .=~ e.g., hthe fieolt ~ J V Ain o 'Mn . ia. a chAm ià or 11he fiber source can be sheared in a, dry s eate, a hydrated state S e.g .
having up to ton percent. by "eight absorbed water), or in a wet :bate, C 'g, having, betwclm about H".. percent s a mil about : ? per e'nt by weight. ~.vater. The fiber s }uirce can even be she red while part alk, or fully submeAged under a liquid, such as sv'stet, ethanol. isopropan<ol.

The fiber '-source can also be she rcdt in under a Ras (Such as a stream or aitmosph i=
of " t t=. c` than air), "\v stye~if or F3wfTi'9~, it ~ i?:t.~-. ,.cis. air), e v,,g., S.>.~~ w~.=S:.i7, or stG''mrm K

Other methods of making the fibrous materials include stone grinding, mechanical ripping or tearing, pin grinding or air attrition milling.

If desired, the fibrous materials can be separated, e.g., continuously or in batches, into fractions according to their length, width, density, material type, or some combination of these attributes. For example, for forming composites, it is often desirable to have a relatively narrow distribution of fiber lengths. In addition, e.g., when making compositions that include bacteria and/or an enzyme, it is often desirable to use a substantially single material as a feedstock.

For example, ferrous materials can be separated from any of the fibrous materials by passing a fibrous material that includes a ferrous material past a magnet, e.g., an electromagnet, and then passing the resulting fibrous material through a series of screens, each screen having different sized apertures.

The fibrous materials can also be separated, e.g., by using a high velocity gas, e.g., air. In such an approach, the fibrous materials are separated by drawing off different fractions, which can be characterized photonically, if desired.
Such a separation apparatus is discussed in Lindsey et al, U.S. Patent No.
6,883,667.
The fibrous materials can be used immediately following their preparation, or they can may be dried, e.g., at approximately 105 C for 4-18 hours, so that the moisture content is, e.g., less than about 0.5% before use.

If desired, lignin can be removed from any of the fibrous materials that include lignin, such as lignocellulosic materials. Also, if desired, the fibrous material can be sterilized to kill any microorganisms that may be on the fibrous material. For example, the fibrous material can be sterilized by exposing the fibrous material to radiation, such as infrared radiation, ultraviolet radiation, or an ionizing radiation, such as gamma radiation.
The fibrous materials can also be sterilized by temperature adjustment, e.g., heating or cooling the fibrous material under conditions and for a sufficient time to kill any microorganisms, or by employing a chemical sterilant, such as bleach (e.g., sodium hypochlorite), chlorhexidine, or ethylene oxide. The fibrous materials can also be sterilized by using a competitive organism, such as yeast against bacteria.

Referring to Figs. 3-8, in some embodiments, the average opening size of the first screen 16 is less than 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than 0.51 mm (1/50 inch, 0.02000 inch), less than 0.40 mm (1/64 inch, 0.015625 inch), less than 0.23 mm (0.009 9a fl`e`a), l:a..ss t .:n 0.20 mm (1.128 ieb, 0.00 8125 inch `ess than 0.18 mix 60,00 inch less than 0.13 mu-t(0.005 Inch), or evE .1 loss than loss t? an 010mm (1/256 i i h, ().003190625 inch). Screen 3.6 is prepared by interweaving moniofl inents 52 having an ap7 opriate di.aiii t.'t to give Jne dae=sired opening s ize. For ex.a iple, the iÃ
Ã:'nofilarÃ' entts be made of a etal, e.g., stainless steel. As the opening sizes get saunter, structural demands on the mono:f laiaients m ti' become greater. For exa uple, for opening siizes less than 0,40 -innn, it can be advantageous to à iake= the screens from monofilamcnis made from a aerial other than stainless steel, e gittaÃinia.ÃTa ` l Vt..l :
y j ~ilt:aliliti,. alloys, "ll.f~;~ F.1-Fa.~Ã'~311.Ã3n..S .Ã3Uta:E.~t, [?liE~.StZ.#' ncc,diurn, rhenia.;1i, ceramics. or glass, In some eÃIib dim :nAts, the screen is mare 3Til Ã
ljas i T i: ! `
3f,t ~+av"i~~? di: getÃiS.=.`* t into .g., cut inthe plate u7i? a w,. C uwf it ~~fa F t` '~ s"..
% lya eJ

In some, embodir'a': ents, the second fibrous 14 is sheaa ed. and passed à r tÃgl ffic. first screen 16, or a different sized screen. In some e Ix-Aimen:. s, the second 'lib oÃ.:s material 114 is pas-sod through õi iab.=G'LilaLa screen having all average open .ice? size L.<li#;.; to, or less than th,~%tt of rrst scree n 16.

Refs i %; to Fig, 9, a third fibrous material 62 can e prep red xrofl.t t:ie , econd fibrous r iater.ial 14 by shearing the second fibrous material 14 and passing the result ng materiall hough a second screen 60 having an average opening size less t;'.-,n the first s e "e , 1~
cellulosic t fl cl:L~dl i`nt ~
FibeT.-sources iÃ:t lud cfiber sourà rsa ,[a~u paper and Paper products cts lilà s..ac4rsi ` t w ~ à if ~ At poi'tr, Ã=z~ate:d paper), Rt llia,t. ` s a. Figs. paper.) and f i_ (Kraft ito lifltÃt fiber sources. including wood, and wood-related materials, e.g., ttaaticl;
board. Other suitable xibi~r sources include natural aber sources, grasses, rice hulls, bagasse, c.att o.n, Jute, hemp, flax, bamboo, sisal, ahaca, straw, corn cobs, rice hulls, coconut i3 i fiber s<?urce=s hi ` 3 to cel.iulose co nt nt. e. ;, cotton; synthe'til`y -1'#be so roesõ C ` ., extÃ'LÃ+. ed y am (oriented yarn or uõ-oriented yarn) or carbon fiber sources: inorganic, fiber sources; and ti Vial fiber source's.. Nat ral or synthetic fiber sources can be obtained from fi girl scrap textile 4 ral `"C c When ~x:tÃ.. ,tlr_a,..aata,.~s? e.g., aa.2.at:5lsa'iii`S or they can be post LdariSÃ.a.1lit-r waste, 4M.t ~., i<#hM. paper , products are used. as fiber sources, they can be virgin ateriaal ;, e.g scra vir,in materials, or they can be post- onsu_rncr w<ste. Aside. from it i t i4l::n.aterials, p o&
cu. astam :~ , ;'=Ei industrial tL ofr l). and pruc "'SIu waste ( .g., effluent from paper Processing) Car, "Aso be used as fiber sources, Also., the fiber source can. be obtained or derived turn human u.y ` t rage), animal or plant wastes. Additional fiber sources hate l' en described iii U.S.
tip Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105.
Blends of any of the above fibrous sources may be used.

Generally, the fibers of the fibrous materials can have a relatively large average length-to-diameter ratio (e.g., greater than 20-to-1), even if they have been sheared more than once. In addition, the fibers of the fibrous materials described herein may have a relatively narrow length and/or length-to-diameter ratio distribution.
Without wishing to be bound by any particular theory, it is currently believed that the relatively large average length-to-diameter ratio and the relatively narrow length and/or length-to-diameter ratio distribution are, at least in part, responsible for the ease at which the fibrous materials are dispersed in a resin, e.g., a molten thermoplastic resin.
It is also believed that the relatively large average length-to-diameter ratio and the relatively narrow length and/or length-to-diameter ratio distribution are, at least in part, responsible for the consistent properties of the fibrous materials, the predictable rheology modification the fibrous materials impart on a resin, the ease at which the combinations of the fibrous materials and resins are cast, extruded and injection molded, the ease in which the fibrous materials pass through small, often torturous channels and openings, and the excellent surface finishes possible with molded parts, e.g., glossy finishes and/or finishes substantially devoid of visible speckles.

As used herein, average fiber widths (i.e., diameters) are those determined optically by randomly selecting approximately 5,000 fibers. Average fiber lengths are corrected length-weighted lengths, BET (Brunauer, Emmet and Teller) surface areas are multi-point surface areas, and porosities are those determined by mercury porosimetry.

The average length-to-diameter ratio of the second fibrous material 14 can be, e.g. greater than 8/1, e.g., greater than 10/1, greater than 15/1, greater than 20/1, greater than 25/1, or greater than 50/1. An average length of the second fibrous material 14 can be, e.g., between about 0.5 mm and 2.5 mm, e.g., between about 0.75 mm and 1.0 mm, and an average width (i.e., diameter) of the second fibrous material 14 can be, e.g., between about 5 m and 50 gm, e.g., between about 10 m and 30 pm.

In some embodiments, a standard deviation of the length of the second fibrous material 14 is less than 60 percent of an average length of the second fibrous material 14, e.g., less than 50 percent of the average length, less than 40 percent of the average length, less than 25 percent of the average length, less than 10 percent of the average length, less than 5 percent of the average length, or even less than 1 percent of the average length.

11a In some embodiments, a Bi"T surface area of the second fbro,,ks lateri al 14 is e.g., greater than 0.25 ? rte, greater than 0.5 mI 2/g, ;y,t ater t w<? .i,' greater than. 0-11 , n i , cs greater t t ali 5 I1 `' "' than 1. 75 131 cx greater ti I`ii1 `i x 1-'12/ `~
t , titer thtl r-:; z gY greater 'tz an .lTa greater F ,a h_,`c?. 60 4,.
W ~, tF. ,, gre,z`ter than 25 ail les r ~. glea:e:r than 35 m r' ea ..I than 5t ,~. ~.. g t. ,3 60 l h eawr ,?.IT, ;' i?~ .'mss IF ater than 1 lOt) 111 % ?, greater than 15 fa fix[ a ' than 200 I$`:} or even greater than, 250, t1 },"g, A porosity of the second hi?.r Fug mate'iÃal

3.4 can be, greater than 20 p 'rent, greater than 25 percent, greater than 35 percent, greater `t ?an 50 1 p.I_ 60 T`r~;I.C.:.: > aE, greater 1'.ia.l1 r#~ tan 70 penes, e.g, =a-`~
E..O.~.i~itr , is .I,,;t~.:z t,l ~~I'i.al'~~.I than 80 i3s`,'.IcLA, greater than S5 t3crcent greater than 90 percent, greater than 92 percent, greater than 94 e. : =tt f -f. >.t ~=r. than ` -a a Rt (F tt a"a n 5 t=_FZ a a (. ! r or a , p E.ent, t,z e at<: . p rc.s.la. 1.,<It i than } E e percent, 1,3 ..:i"
x.icz.: }_ # or I `' :F;
greater than 99.5 p rce#3t.

in some embod1 rents, a ratio of the average l ngth- o diameter ratio of the first fibrous material 12 to the average length-to-diameter ratio of the second 11bro s material 14 iL e.g.' less than 1 .5, e.g., less than 1.4. less than, I.25, less than. `,1.
less than 1,0:5, less c. 11 s i 1.05, less t. tan 13,025, or even substantially equal to 1.

In par .le..,:#iar emuod.Imeznts, to second fibrous material 14 is sheared again and the resulting fibrous mate r ral passed through a second screen. having an average opening size less than the 151st screen to provide a third fibrous material $2 In such instanc s, aI ratio of the a:. {,xrage longth to dialer 'r ratio of à e second t,s..nateI al 14 to the avtfragge length 20' to diameter ratio` of the third 1. brous material. 62 can be e.g., less than 1.5, e ti;., less: tha 1. less t4 an 1.25, or even less h n 1.1.

In sonic :. ^ I aliment , the third fibrous material 62 is passed through a third ; creei, to t?rod.tiCC a ?bunt fihrouus material. The 1?berth felbrous material :a be, o.&, passed through a ltnirt,i si reen to produce a fifth material. Similar screening processes can be 25 repeated s.s an y timnios as desired to produce the desired, fibrous material having the desired pro ernes.

In some ennbodime Its, the desired fibrous material in 1 fiber,; having an average `.k lt-t 1 T<LI1: c=#.l1 ratio i} greater than 5 and having a standard deptia:on o the f bC r eI g ffi ii .q))ql'ACa.~ is less than Sixty percent t of t~.1`tr'cl~/Ã.'Ii~yC=I1y:1p2gt"~, For S:'=K.i]r1~31~.', .~lt=ca`lti%G~c.~;C'~lt'.'1'i`~ t:l-yt)5-.greatey~ }. than 25 E . greater than S, . and the cC# {.3am et .w ratio can be greater t' than 0/f e.&' a~.c {i.1j ?,,:? '..x 6.: i:?1 c. 1 t1``t,-iil about I.I.5 nun and ,?..?
5m.,..ye. ., between about 0.75 1 aim and 1.0 mm. An average widen of the fibrous material can be between :about. 5 um and 50 unir e t between about 1 ? pivn and 30 pnn, For e?:i n.iple, the ,standard deviation, can be le s than 50 percent of the average length, e.g., less than 40 percent, less than 30 percent, less than 25 percent, less than 20 percent, less than 10 percent, less than 5 percent, or even less than 1 percent of the average length. A desirable fibrous material can have, e.g., a BET surface area of greater than 0.5 m2/g, e.g., greater than 1.0 m2/g, greater than 1.5 m2/g, greater than 1.75 m2/g, greater than 5 m2/g, greater than 10 m2/g, greater than 25.0 m2/g, greater than 50.0 m2/g, greater than 75.0 m2/g, or even greater than 100.0 m2/g. A desired material can have, e.g., a porosity of greater than 70 percent, e.g., greater than 80 percent, greater than 87.5 percent, greater than 90 percent, greater than 92.5, greater than 95, greater than 97.5, or even greater than 99 percent. A particularly preferred embodiment has a BET surface area of greater than 1.25 m2/g and a porosity of greater than 85 percent.

FIBROUS MATERIAL/RESIN COMPOSITES

Composites including any of the fibrous materials or blends of any of the fibrous materials described herein (including any of the fibrous materials disclosed in U.S. Patent Nos. 6,448,307, 6,258,876, 6,207,729, 5,973,035 and 5,952,105), e.g., the first 12 or second fibrous material 14, and a resin, e.g., a thermoplastic resin or a thermosetting resin, can be prepared by combining the desired fibrous material and the desired resin. The desired fibrous material can be combined with the desired resin, e.g., by mixing the fibrous material and the resin in an extruder or other mixer. To form the composite, the fibrous material can be combined with the resin as the fibrous material itself or as a densified fibrous material that can be re-opened during the combining. Such a densified material is discussed in International Publication No. WO 2006/102543.

Examples of thermoplastic resins include rigid and elastomeric thermoplastics. Rigid thermoplastics include polyolefins (e.g., polyethylene, polypropylene, or polyolefin copolymers), polyesters (e.g., polyethylene terephthalate), polyamides (e.g., nylon 6, 6/12 or 6/10), and polyethyleneimines.
Examples of elastomeric thermoplastic resins include elastomeric styrenic copolymers (e.g., styrene-ethylene-butylene-styrene copolymers), polyamide elastomers (e.g., polyether-polyamide copolymers) and ethylene-vinyl acetate copolymer.

In some embodiments, the thermoplastic resin has a melt flow rate of between 10 g/10 minutes to 60 g/10 minutes, e.g., between 20 g/10 minutes to 50 g/10 minutes, or between 30 g/10 minutes to 45 g/10 minutes, as measured using ASTM 1238.

13a IM some embodiments, compatible blends of any oftlie ; bt`_tw flicianoplxstÃc resi.ns ca ii be used.

In some embodiments, the thermoplastic resin has a pol d spas. index (P11)1), ix-.
zi i aitio of the weight average molecular weight to iI? . E~wEiT b s'< 3"s 4 molecular ~z= E i of treater than 1.5, e.g. greater than 2.0 greater than 2.:Z greater than 5Ø %
rt or oven greater than 10Ø

f In speci,icc mbodimeÃ#Ãs, poly'oieins or blends of po olefin, are at i ized as the tie mo l s i_ c resin-.., t'} xa mp,es c "f thermosetting, resins include natural rubber, b' , adien+.
rubber and In addition to the desired fibrous ià atcriai and rein, additives, e.g , in the form of a, solid or a liquid, c azn be added to the combination of the Iibruus materia .
and .esin. Fo example, s itable additives include tillers such as calciu :aibonatt graphite, -v ollasi rite, micca, glass, filacr glass, s'. eia, and talc; inorganic flame retardant` such as, alumina # Ãtitiii'i3tc' or mUgnà sizinn 1y4. roxi' e;; organic t `.fine retardants such as c i1orinated or bioi,t#nated organic compounds; ground Consttuc.tion Waste, ,,rou it; tire rubber, cai"b'xi ft rs or, #ietal tà ers or powders ahaninum, s tainless steel). These additives can 'ein.,bre extend, or i lane electrical. mechanical or compatibility properties, Other aiditi t'es include fragi inec's, cm1pling agent, compa ihiliizers, poi p onylene, 20 processing aids, lubricants, v&, fluorinated polyethylene, plasticizers, an' ioxidants, opacif.eis, heat stabilize s, colorants. foaming agents, impact odife s, polymers, e.g.9 d33e`;raÃaable polyin ri, ph o biocides, antistatic agents, e.g., ;tai c.rzt`s or ?_thox 'i5 fed fat a0=id <i.i2'iines. Suitable antistatic compounds is etude carbon blacks, carbon fibers, Tnetal. tillery`s.(cationic ( comp #,n nds) e,, quatgernmr`!{

25 co-mlxmnds, e.;] , i \ chioro~ Li R r xypro Ja t i:31 v)S i~iT .S23~_wl ium t'1 lori at=

i ikanolemides. and arnines. Representative degradable polymers include p lyh;
drox. j, Ads, e ' . p{'..'s l a. ti cs, pok'i glycol des and c:opolyine of lactic cid and glycolic acid~
poiyth `idi('x %h#.stynr acid), - 7\ai it)Y b ~c r e c''-:t<. , oly[la :t`iL
~' # G . :3r tact dY e;j.
poly[ gi yi olide co-(e-eapmlactone)], .p lycarhonates, poiy(ami.so acid, *

s ~~ vdroxyÃa11~ Ã at polya ihydrides, polyorthoesters one blends ofÃhese polymers.
In some embo iments. the fibrous mate gal is ste]i i.zed prior to combining w'ith a resit` to kill an `microorganisms that may be on the f m:F:ti:i iateriall. For exa'naple, the fibrous material can he sterilized by exposing the fibrous material to adiation by hotting, the fibrous material under conditions and for a sufficient time to kill any microorganisms, e.g., boiling at normal atmospheric pressure; or by employing chemical sterilants.

It can be advantageous to make the composite smell and/or look like natural wood, e.g., cedarwood. For example, the fragrance, e.g., natural wood fragrance, can be compounded into the resin used to make the composite. In some implementations, the fragrance is compounded directly into the resin as an oil. For example, the oil can be compounded into the resin using a roll mill, e.g., a Banbury mixer or an extruder, e.g., a twin-screw extruder with counter-rotating screws. An example of a Banbury mixer is the F-Series Banbury mixer, manufactured by Farrel.
An example of a twin-screw extruder is the WP ZSK 50 MEGAcompunderTM, manufactured by Krupp Werner & Pfleiderer. After compounding, the scented resin can be added to the fibrous material and extruded or molded. Alternatively, master batches of fragrance-filled resins are available commercially from International Flavors and Fragrances, under the tradename PolylffTM or from the RTP Company. In some embodiments, the amount of fragrance in the composite is between about 0.005 %
by weight and about 10 % by weight, e.g., between about 0.1 % and about 5 % or 0.25 %
and about 2.5 %.

Other natural wood fragrances include evergreen or redwood. Other fragrances include peppermint, cherry, strawberry, peach, lime, spearmint, cinnamon, anise, basil, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus, pine, fir, geranium, ginger, grapefruit, jasmine, juniperberry, lavender, lemon, mandarin, marjoram, musk, myrhh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, new car or mixtures of these fragrances. In some embodiments, the amount of fragrance in the fibrous material-fragrance combination is between about 0.005 % by weight and about 20 % by weight, e.g., between about 0.1 % and about 5 % or 0.25 % and about 2.5 %. Even other fragrances and methods are described in International Publication No. WO
2006/12543.

Any of the fibrous material described above, e.g., the first 12 or second fibrous material 14, together with a resin, can be used to form articles such as pipes, panels, decking materials, boards, housings, sheets, blocks, bricks, poles, fencing, members, doors, shutters, awnings, shades, signs, frames, window casings, backboards, flooring, tiles, railroad ties, trays, tool handles, stalls, films, wraps, tapes, boxes, baskets, racks, casings, binders, dividers, walls, mats, frames, bookcases, sculptures, chairs, tables, desks, toys, games, 15a pallets wharves. ~ ~ ,r, ? , boats, il7:a.S1S, septic tMirik`. automotive panels, computer housings, s 3i3 `v and ii tow.- o Lind electrical casings, fu ÃaÃtur ., i picnic tabl s= bench-s, sh It r trio:!
s Mangers. servers. book covers, cares, crutches, insulation, thread. clot, riovElties, house wares and structures.

T lie fibrous '1 1aterial may be dyed before combining with the rosin and compounding to foi`.it1 the composites described above. In some embodiments, this dy;eeii7g c in be helpful in i'aas i#3e or la dJ rig ti1e fibrous material, +espe4udlS' Y irge i :gl"',i331' ctt3:Ãot-is ol. t h : fibrous, materiall in molded or extruded parts. Such a when pr sent in relatively high LE?i3centi't ~ilons can show -up as speckles in .he surfaces of t1he.molded or extruded parts, For example, he d :sired fibrous material can be dyed using an acid dye, diÃec dye or ti. re3:ctive dye. Such dyes are available from Spectra Dyes. Kearny. NJ or Keystone aniline Corp<mtion, Chic go, 11- Specific examples of dyes include S ECTRA"m LIGHT
Y1..LLOW 20, SPE;C.TRACID" k' YELLOW 4 GL CONC 200, SPEC, a'RANYIYM
SET
R 1ODAMINF. 5, SPEC T AMYL M NEUTR:. L RED B.
P ECTRAMIN N n.
BENZOPE' 'URINE, S P(:TR A. )lA ` ` BLACK. 013, SPECTRA \'.IINIUM
'11) RQl10IS E 0, and S P E 1 R A:N41N E M GR;: Y 1,VI, 200%, eac} being available from Spei~ctra Dyes .

In some eil bt ; meats, resin color concentrates pig tints are blended 2D with dyes. %k } z ;i su E blends are then compounded, ith the desired fib o.i.s inat.riial, Ã .e Sit us 'Ã aterial i:3 i Y be dyed in-sit during the compound ng. Color C _} 1L
=ntrat s are s:.~ 1iz'*=2]3L. e3a+.3i~t31'isi:a.I~t., l"_.XA MPE ES

25 Scanning electron .i7.`,,iS:i 33 7Ã:I7las were obtained on a JEOL 65000 field E' 13, s ion sC:amn.io electron ` lcroscope. Fiber l ongths and widths (i.L=, diameters) a eie= deter33`Ã.ined:
by integrated Paper Services, IIic. , A pit it o. \V i US , an automated a1? a l .e (TAPPI
T2'71), BET surf.3cc area was determined by k1licio.-T critics Analytical Services, as were po osik i` ii;l ulk density.

tar~i'fton O Fibrous; NI.a. iital F3'o i Polv."CSated1.P L er A 1 500 Bound skid of virgin, liai fgallon juice cartons nmd of it:=i prin`1ed nolycoated white Kraft hoard having a bulk density' of 2Ã0 lb:/f was obtain; d from 1t international Paper. The .material was cut into pieces 8 I..4 inches by i I
inches using a guillotine cutter t^ id fb to a '.' t5 1unson rotary Lknitfe~ cutter, Model SC 30.3 Model SC {O is C
equipped with tihur rot try blades, four fixed blades, and a discharge s,;;..reen . wa4'~ing 1 if inch openings. The gap between the rotary and fixed blades was set to approximate) 0J)20 inch. The rotary knife cuttt ..v:3~,>ed the confetti-like pieces( across he knife-edges, tearing the nieces apart and releasing a fibrous material at a rate of about one pound per hour. The fibrous material had a BET surface area of 0,9748 rl- 1/fig 1 0.0167 y g, a Porosity o l., pf 89.04`7 :if.rc\nt and a bulk density ( O.53 psia of 0. F260 g niL. An avw,~' ge iena tw of 2\ fl, s k fibers was i .J 11 .1.41 Ãt-tI3 and average aaverage width of the fibers was 0.02" g1v3 1.4; an II`'.`ic,i.3;

nuucr1rF z grt<lphs the c r .t,a. to c are shown > a l t1br{ 3ta~3Ã s an d I.> at ~5 > magnification and 1000 X ma ificat on. resne tn' t'`, Ja r3 I? I iC3?c rLiti 13.3 Of ibro ~'iii'=t 3c3ti From Bleached Kraft Board A 1500 pound skid of v-,-gin bleached white Krafi board I av i>3 Y a bulk density ol f 1I?= It as ~.`btane .ITom In te +.l :t<3. al Paper. The material 'x.15 =11:t.
into ÃÃ of s 8 :1# 1 es by I l : nch :s using a;.;uillo ine cutter and fed to a Munson rotar- ? knife cutter. Model SC #..
The discharg screen had 1 /8 inch opelnings. 'File gap ba w ee the rotary and ta: i blades was set to approximately 0,020 inch. The rot:ry:nil` cutter sheared the, coiifeffi -like i es. es, releasing a fibrous irr . YaI aI. a rate of about one pound per hour. a lie fibrous 20 material had a BET surface area of 1, 1316 ~ ~> , ' . .I11 i1 rte , w it rosin s3A'' .r 285 percent j r '@,-.0, 5 v t; 1~-~` r 4i + ` is1 .~: . <`~, 3 1 average I t:=>1 -i l 7 { 3.,a ,t. a bulk ~.>IL ~~[;Y341t~' 13s1 i`3.~ C3 t" ~~~.,.+'~õ,, a3 of F1lbei's was ',,061 n-ni .'n man avera-c width of the fibers was 0,0245 trin3, giving an average L/t) of '"3:l , Scanning electron micrographs of the. fibrous maters l are shown in igs. 13 and 14 at 25 X magnification and 1000 X magnif cation, respectively.

Pj '" tÃon, O ,,yi :c_ S13oaÃ`Qd 'i rous-4r ate a From l lg= : ` e t3 , I Ãytu ~L _ 3f\
`~ 1.r..` pound { skid of virgin bleached t white j 4''i ar'~ having Y~
density, of S:_!
.5L::,, white .{~Y. 5~3 ~ `)1~i7.r. ~} ii bulk .~` ' .~1.

lb. 3 was obtained from International Paper, The material was cut into Pieces 8 1/4 Ãnehes 30 , I i> the guillotine cutter a fed to a Munson 3"Mary knife cute , Model 8(230.
s sin g a an The discharge screen had I / 16 inch openings. The gap bet.4 eel the rotary .uaQ ixed blades Was, set ral a;<)P'"t~' 5.#1õ.0 ?1iL15; `I'1Lrf~tar~' 1%33i f ; ~:ti>s ~~a... ~ff., ~.i.,t.t~r the :>~'0=t:1-õi"ke pieces, r"ye2.iasi.)rn#', afibrous {omaterial. at a rate of about one pound per.
~y.ou/r. I'll materil estfltin`?

z> ) y oynt the fIyst shear t was ~( .god back into the same setup described 'above ve and siJ.eaTod again.

h resalt.i$ a ei:.rous material had a BET surface area of :.4408.1 O',,W15,61 ig a porosity of 9U998 percent and a bulk density(@U3 psi) of 0,11 298 `F` a.. Ar.
a.`c' is l 84th o ti?e; fibers was 0r 9i rztm and an average width of the fibe was .?
.? 6 f73I1'F ?wing an Fib iai ,.. 'D of 34:1. Scan?_ii electr?r itiF rt?klu ~ s 4} ?L'`
.ibaous'n,materia are 51off.'.n in Pigs. ati16 at 25 X. magnification and 1000 X magnification, respe i v en =

4-Example 4 -:} ..z ..... n OfTbrice Sheared Fibrous Material Po Ble :.}~e&t ra1Ã 3;? _ A 1500 pound skid of virgin bleached white Kra board having a bulk d{ niity of i'i?, ft was obtained from International Paper. The material was cut into pieces 8 ..`~ inche ;Y 1 i r zasi?Z~
= inch"-'s x g a 3 (Yif tt`<I and fed to L~i ~ iFif? siiF rotary i r. t :lai>r S.i 1,i.Etftirii cutter ti7iE_ ; Model , ?:
The =
=Tie_La ch rge screen had 1/8 inch openings. The pp be'tw; ,on tii otar id f xsd blades was set to approximately 0.020 inch. The rotary knife cutter sheared he confetti-like pieces across the ~~i if t= ` t 5:= The material resultiun from the .rst shearing a ibd back into the sa,? e setp and Bile screen was replaced with a l6 inch s.-,aeon. I 'his material was sheave d.
The material 'e i:sting from the second shearing wfl tt.tt into f :t a>?~ F?
<1i1: the screen was replaced with a 1/32 inch screen. The ri.sui:ii#;u}
fibrous material lead a ;,urface area of 1,6897 n:i z hh a .'ss a, Porosity of 1 r 3 `?~.rs =r?t i?$7 F 'ii.i tten sit (a,0, i? T:a) o f}, i i s t .:: tt n N a[ L a}g t i 3 n1 o TD'` `
fibers was 0.324 it in and an avenge width of the fibers was 0.0262 inin, giving al.~ average 91 g `. t?: ?' i; ing electron mierographs of the fibrous material are shown in Figs. I7 and l s' at 25 magnification and 100) X Triapfficati.ovi, respectively O J ER COMPOSITIONS AND USES OF THE . I ROUS MAJITRJAL

Compositions can be prepar : that iriclude any oft-he fibrous Material", described 25 herein, incikidin4 any of the fibrous materials, resins, additives or other c ) mponents -,closed in L:.s. Patent Nos, 6,448,307, 6,258,87 , 63 2,07, t 2t3 5,973,03 S
and 952,1 (05), For example. any of the fibrous materials described herein can. he combined with a solllid, i liquid or a . z v; a a chemical i.i chemical tt) fFki 4it5Fi (in the,olid or liquid statti),as is i`,?armaceutit it t=e.cx an antibiotic), : n aagi'ic-Lift raI material 4 t'.. .; plant seeds, a fertilizer.

JL herbicides C>z peso i i 3, or an enzyme Or as formulation ti at includes en'< rocs. Co ltpositl iris that ~(iin =ludee one or more type of bacteria or bacteria 1-n cor binatiosK with one or rfior'e enf`Ymess can also be prepared.

S

Such compositions can take advantage of the fibrous 'materia s iesin<&1le pÃope rties.
For example, an of the t brous matct. `i.F._ s um he used to absorb chemicais, pcot 3t;a!iy z3`'SZ?.i 3in l times their ow weigh For example, It fibrous "nF3tericit can be used absorb spilled oil; or other chemicals,, Comb Sling those fibrous materials , i -#. a xicr e gaE isila, such as a bacteiiitun, that can ni tabolize t hte oil or chcn- ical can aid in cleanup. For >sxaia illy the fibrous. ma .erials can be combined with solutions .3a e nzymes, dried, ..z, .?..., used in pot bedding, or combined with a pharmaceutical and us d for delivering a therapeutic agent, such as a drug. If desired, the ab Ãs i'l a i.als ~ ~ be combined with a d yititl.i 3C ~~y's3~bL`Ã eri a as olygl4 .t..1#.c aitcid, .
ofyltactr :.ti.' acid 3`.e3,,d F' `.4 =<. N . ..
and 'i 0 copol ni3. } `` . s {: f glycnl.Ã# aallactic acid. Other degradable materials that can be used sed }' a l C

been i cuss ? a ove, c onmosÃtions that include fibrous materials, C 'g., ceiilÃdoslc or L:?Foced F tti# :
materials and, e .g., chemical;, or chemical forilliiir_Ftions. in the solid, liquid or gaseous st..ite,, can be prepared. e.g,,, in ViiÃous iilunersioll, spraying, or blending apparatuses, For t~ exanipli tae compositions can be prepared us nq ribbon blenders, cone ble.n ers, double cone blenders, and Patterson-Kelly W" blenders.

if des red, lignin can be removed from any of the fibrous l > iia `,` lat include lignin, 3, ch as Fr;ilt3c eli:ll;,1S t i l iterial , Also, if desired, the fibrous la e.. Ãal can be sterilized to kill any inic=roorganisins that. iiis y be on the fibrous m3 .ate,i<al. ,For example, the 20 air rouss materiail can >be sterilized by exposing the Jfpbrous i uttetial ".t. iadiat lion, such as infrared iadi tion, ultraviolet rady ia iooi ,) or an i01117i radiation,{ such as gamma .radiation.

i)1. 'h can also be sterilized by cheating the l braus nuac ial undeyr conditions and t'or a sufficient time'. to kill any 1 I.s :P'C3Lt.F' ?elil:i siTl , or by 'l plo i # a chemical sterih t, such as bleach (C,;.;'., sodium hypochlori_t), chiorhex dine, or ethylene oxide.

Any of the fibrous materials can be `washed, c:s , with a .iQu.id such as water, to, remove ;yundesirabl impurities anrf for L ontClmin ilia :.

In a -specific appl:ratioÃ` the fibrous- material, can be. usod as af;;.odstook for various 31`ivF'd33rg #FY 3 ià , Such as yeas and bacteria, that can '.E i`mei:t or otherwise work on '3.t-it fibrous nlatert ear to produce a useful material, such as a fuel e.g. art alcohol, an organic a, hydrocarbon (. -ydi, igei,, or ~_ rote,' l.i e al:coholll produced can be a monohydroxy alcoho51 c;F'... ethanol, rat a, 3 3 41 3'?alb v S' :1.ti C3hol, t Y~, ethylene glycol or glyc _.rin. Ex n ?.'es of alcohols.- .tt: s an produced include anethanol, .t'n~rlll 3F"{3i~<1iÃf}ai, isop L>f iai ol, its tia33, ethyl ethylene co propylene glycol, 1,4-butane diol, glycerin or mixtures of these alcohols. The organic acid produced can a monocarboxylic acid or a polycarboxylic acid. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid, y-hydroxybutyric acid or mixtures of these acids. The hydrocarbon produced can be, e.g., an alkane or an alkene. Examples of hydrocarbons that can be produced include methane, ethane, propane, isobutene, pentane, n-hexane or mixtures of these hydrocarbons.

In a particular embodiment, a fiber source that includes a cellulosic and/or lignocellulosic fiber source is sheared to provide a first fibrous material. The first fibrous material is then passed through a first screen having an average opening size of about 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material. The second fibrous material is combined with a bacterium and/or enzyme.
In this particular embodiment, the bacterium and/or enzyme is capable of utilizing the second fibrous material directly without pre-treatment to produce a fuel that includes hydrogen, an alcohol, an organic acid and/or a hydrocarbon.

In some embodiments, prior to combining the bacteria and/or enzyme, the fibrous material is sterilized to kill any microorganisms that may be on the fibrous material. For example, the fibrous material can be sterilized by exposing the fibrous material to radiation, such as infrared radiation, ultraviolet radiation, or an ionizing radiation, such as gamma radiation. The microorganisms can also be killed using chemical sterilants, such as bleach (e.g., sodium hypochlorite), chlorhexidine, or ethylene oxide.

In a particular embodiment, the cellulosic and/or lignocellulosic material of the fibrous material is first broken down into lower molecular weight sugars, which are then added to a solution of yeast and/or bacteria that ferment the lower molecular weight sugars to produce ethanol. The cellulosic and/or lignocellulosic material can be broken down using chemicals, such as acids or bases, by enzymes, or by a combination of the two. Chemical hydrolysis of cellulosic materials is described by Bjerre, in Biotechnol.
Bioeng., 49:568 (1996) and Kim in Biotechnol. Prog., 18:489 (2002).

Bioethanol strategies are discussed by DiPardo in Journal of Outlook for Biomass Ethanol Production and Demand (EIA Forecasts), 2002; Sheehan in Biotechnology Progress, 15:8179, 1999; Martin in Enzyme Microbes Technology, 31:274, 2002; Greer in BioCycle, 61-65, April 2005; Lynd in Microbiology and Molecular Biology Reviews, 66:3, 506-577, 2002; Ljungdahl et al. in U.S.
Patent No. 4,292,406; and Bellamy in U.S. Patent No. 4,094,742.

Referring now to Fig. 19, a fibrous material having a low bulk density can be combined with a microorganism, e.g., freeze-dried yeast or bacteria, and/or a enzyme, and then revertibly densified to a fibrous material composition having a higher bulk density. For example, a fibrous material composition having a bulk density of 0.05 g/cm3 can be densified by sealing the fibrous material in a relatively gas impermeable structure, e.g., a bag made of polyethylene or a bag made of alternating layers of polyethylene and a nylon, and then evacuating the entrapped gas, e.g., air, from the structure. After evacuation of the air from the structure, the fibrous material can have, e.g., a bulk density of greater than 0.3 g/cm3, e.g., 0.5 g/cm3, 0.6 g/cm3, 0.7 g/cm3 or more, e.g., 0.85 g/cm3. This can be advantageous when it is desirable to transport the fibrous material to another location, e.g., a remote manufacturing plant, where the fibrous material composition can be added to a solution, e.g., to produce ethanol. After piercing the substantially gas impermeable structure, the densified fibrous material reverts to nearly its initial bulk density, e.g., greater than 60 percent of its initial bulk density, e.g., 70 percent, 80 percent, 85 percent or more, e.g., 95 percent of its initial bulk density. To reduce static electricity in the fibrous material, an anti-static agent can be added to the fibrous material. For example, a chemical anti-static compound, e.g., a cationic compound, e.g., quaternary ammonium compound, can be added to the fibrous material.

In some embodiments, the structure, e.g., bag, is formed of a material that dissolves in a liquid, such as water. For example, the structure can be formed from a polyvinyl alcohol so that it dissolves when in contact with a water-based system. Such embodiments allow densified structures to be added directly to solutions, e.g., that include a microorganism, without first releasing the contents of the structure, e.g., by cutting.

OTHER EMBODIMENTS

While certain embodiments have been described, other embodiments are possible.

While some embodiments use screens to provide a desired fibrous material, in some embodiments, no screens are used to make the desired fibrous. For example, in some embodiments, a fiber source is sheared between a first pair of blades that defines a first gap, resulting in a first fibrous material. The first fibrous material is then sheared between a 21a second pair of t'lia`t define a socond gap that .Ãs smaller than `. 1e first lap, resulting i t?
Second fibrous material. Sinliklr screening processes ca be à e caWd as à an r t Ã,T~t s as desr od to produce hedesired fibrous material having the desired properties.

In some en bodiments, a ratio of all average ratio first fibrous material to, an a cri>gõ lcngth-to-diameter of the Second fibrous material s Iu s than.
I . ?, Still 3 ,i I '1 bod ,l~tz 4 c3Ã within the Scope of the t bllowing claims.

'3 7

Claims (7)

CLAIMS:

1. A method of making a fuel, the method comprising:

shearing a fiber source that is a cellulosic or lignocellulosic material to provide a first fibrous material;

passing the first fibrous material through a first screen having an average opening size of about 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material; and combining the second fibrous material with a bacterium and/or enzyme, the bacterium and/or enzyme utilizing the second fibrous material to produce a fuel comprising hydrogen, an alcohol, an organic acid and/or a hydrocarbon;

wherein the second fibrous material has a BET (Brunauer, Emmet and Teller) surface area of greater than about 0.25 m2/g and a porosity of greater than 25%

2. The method of claim 1, wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, 1,4-butane diol, glycerin, and mixtures thereof.

3. The method of claim 1 or 2, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, lactic acid, .gamma.-hydroxybutyric acid and mixtures thereof.

4. The method of any one of claims 1 to 3, wherein the hydrocarbon is selected from the group consisting of methane, ethane, propane, isobutene, pentane, n-hexane, and mixtures thereof.

5. The method of any one of claims 1 to 4, wherein the second fibrous material has a BET (Brunauer, Emmet and Teller) surface area of greater than about 1.25 m2/g.

6. The method of any one of claims 1 to 4, wherein the second fibrous material has a porosity of greater than about 85 percent.

7. A method of making a fuel, the method comprising:

shearing a fiber source that is a cellulosic or lignocellulosic material to provide a first fibrous material;

passing the first fibrous material through a first screen having an average opening size of about 1.59 mm or less (1/16 inch, 0.0625 inch) to provide a second fibrous material having a BET (Brunauer, Emmet and Teller) surface area of greater than about 0.25 m2/g and a porosity of greater than 25%;

hydrolyzing the second fibrous material to provide a hydrolyzed material; and combining the hydrolyzed material with bacterium and/or enzyme, the bacterium and/or enzyme utilizing the hydrolyzed material to produce a fuel comprising hydrogen, an alcohol, an organic acid and/or a hydrocarbon.