U.S. patent application number 16/560463 was filed with the patent office on 2020-07-02 for processing biomass to obtain hydroxylcarboxylic acids.
This patent application is currently assigned to Xyleco, Inc.. The applicant listed for this patent is Xyleco, Inc.. Invention is credited to Jihan Khan, Thomas Craig Masterman, Marshall Medoff, Jaewoong Moon, Andrew Papoulis, Robert Paradis.
Application Number | 20200208180 16/560463 |
Document ID | / |
Family ID | 51792517 |
Filed Date | 2020-07-02 |
United States Patent
Application |
20200208180 |
Kind Code |
A1 |
Medoff; Marshall ; et
al. |
July 2, 2020 |
PROCESSING BIOMASS TO OBTAIN HYDROXYLCARBOXYLIC ACIDS
Abstract
Biomass (e.g., plant biomass, animal biomass, and municipal
waste biomass) is processed to produce useful intermediates and
products, such as hydroxy-carboxylic acids and hydroxy-carboxylic
acid derivatives.
Inventors: |
Medoff; Marshall;
(Brookline, MA) ; Masterman; Thomas Craig;
(Rockport, MA) ; Papoulis; Andrew; (Canton,
MA) ; Moon; Jaewoong; (Andover, MA) ; Khan;
Jihan; (Cambridge, MA) ; Paradis; Robert;
(Burlington, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Xyleco, Inc. |
Wakefield |
MA |
US |
|
|
Assignee: |
Xyleco, Inc.
Wakefield
MA
|
Family ID: |
51792517 |
Appl. No.: |
16/560463 |
Filed: |
September 4, 2019 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14786388 |
Oct 22, 2015 |
10501761 |
|
|
PCT/US2014/035467 |
Apr 25, 2014 |
|
|
|
16560463 |
|
|
|
|
61816664 |
Apr 26, 2013 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 67/28 20130101;
C08L 97/02 20130101; C12P 7/46 20130101; C12P 2201/00 20130101;
C12P 7/625 20130101; C12P 7/48 20130101; C08L 1/02 20130101; C08L
67/04 20130101; C08G 63/06 20130101; C08L 3/00 20130101; C08K 5/06
20130101; C08G 63/08 20130101; C08G 63/78 20130101; C08K 5/11
20130101; B01J 2219/24 20130101; C08K 3/346 20130101; C12P 7/42
20130101; C08K 2003/387 20130101; C08K 3/34 20130101; C08K 3/04
20130101; C08K 3/38 20130101; C12P 7/56 20130101; B01J 19/24
20130101; C08K 3/36 20130101; C08K 3/04 20130101; C08L 67/04
20130101 |
International
Class: |
C12P 7/56 20060101
C12P007/56; C08G 63/78 20060101 C08G063/78; C08G 63/06 20060101
C08G063/06; C12P 7/48 20060101 C12P007/48; C12P 7/46 20060101
C12P007/46; C12P 7/42 20060101 C12P007/42; C12P 7/62 20060101
C12P007/62; C08L 97/02 20060101 C08L097/02; C08L 67/04 20060101
C08L067/04; C08L 3/00 20060101 C08L003/00; C08L 1/02 20060101
C08L001/02; C08K 5/11 20060101 C08K005/11; C08K 5/06 20060101
C08K005/06; C08K 3/38 20060101 C08K003/38; C08K 3/36 20060101
C08K003/36; C08K 3/34 20060101 C08K003/34; C08K 3/04 20060101
C08K003/04; C07C 67/28 20060101 C07C067/28; B01J 19/24 20060101
B01J019/24; C08G 63/08 20060101 C08G063/08 |
Claims
1. A method for making a product comprising: treating a reduced
recalcitrance lignocellulosic or cellulosic material with one or
more enzymes and/or organisms to produce an alpha, beta, gamma
and/or delta hydroxy-carboxylic acid, and converting the alpha,
beta, gamma and/or delta hydroxy-carboxylic acid to the product.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 14/786,388, filed Oct. 22, 2015, which is a National Stage
entry of International Application No. PCT/US2014/035467, filed
Apr. 25, 2014, which claims priority to U.S. Provisional
Application No. 61/816,664, filed Apr. 26, 2013, which are
incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] Many potential lignocellulosic feedstocks are available
today, including agricultural residues, woody biomass, municipal
waste, oilseeds/cakes and seaweed, to name a few. At present, these
materials are often under-utilized, being used, for example, as
animal feed, biocompost materials, burned in a co-generation
facility or even landfilled.
[0003] Lignocellulosic biomass includes crystalline cellulose
fibrils embedded in a hemicellulose matrix, surrounded by lignin.
This produces a compact matrix that is difficult to access by
enzymes and other chemical, biochemical and/or biological
processes. Cellulosic biomass materials (e.g., biomass material
from which the lignin has been removed) is more accessible to
enzymes and other conversion processes, but even so,
naturally-occurring cellulosic materials often have low yields
(relative to theoretical yields) when contacted with hydrolyzing
enzymes. Lignocellulosic biomass is even more recalcitrant to
enzyme attack. Furthermore, each type of lignocellulosic biomass
has its own specific composition of cellulose, hemicellulose and
lignin.
SUMMARY
[0004] Generally, this invention relates to methods and processes
for converting a material, such as a biomass feedstock, e.g.,
cellulosic, starchy or lignocellulosic materials, to useful
products, for example, hydroxy-carboxylic acids (e.g., alpha, beta.
gamma and delta hydroxy-carboxylic acids) and derivatives of
hydroxy-carboxylic acids (e.g., esters). Such hydroxy-carboxylic
acids can be poly-hydroxy-carboxylic acids, e.g. di-, tri-, tetra-,
penta-, hexa- hepta- and octa-hydroxy carboxylic acids. The
poly-hydroxy-carboxylic acid can be substituted with other groups,
e. g. alkyl groups. The carbon chain of the carboxylic acid can be
straight chained, branched, cyclic, or alicyclic.
[0005] In one aspect the invention relates to a method for making a
product including treating a reduced recalcitrance biomass (e.g.,
lignocellulosic or cellulosic material) with one or more enzymes
and/or organisms to produce a hydroxy-carboxylic acid (e.g., an
alpha, beta, gamma or delta hydroxy-carboxylic acid) and converting
the hydroxy-carboxylic acid to the product. Optionally, the
feedstock is pretreated with at least one method selected from
irradiation (e.g., with an electron beam), sonication, oxidation,
pyrolysis and steam explosion, for example, to reduce the
recalcitrance of the lignocellulosic or cellulosic material. Some
examples of hydroxy-carboxylic acids that can be produced and then
further converted include glycolic acid, lactic acid, malic acid,
citric acid, and tartaric acid (disubstituted), 3-hydroxybutyric
acid (beta substituted), 4-hydroxybutyric acid (gamma substituted),
3 hydroxyvaleric acid (beta substituted), gluconic acid (tetra
substituted at alpha, beta, gamma, and delta carbons with an
additional hydroxy at the epsilon carbon).
[0006] In some implementation of the method, the hydroxy-carboxylic
acid is converted chemically, for example, by converting lactic
acid to esters by treating with an alcohol and an acid catalyst.
Other methods of chemically converting that can be utilized include
polymerization, isomerization, esterification, oxidation,
reduction, disproportionation and combinations of these.
[0007] In some other implementation, the lignocellulosic or
cellulosic material is treated with one of more enzymes to release
one or more sugars; for example, to release glucose, xylose,
sucrose, maltose, lactose, mannose, galactose, arabinose, fructose,
dimers of these such as cellobiose, heterodimers of these such as
sucrose, oligomers of these, and mixtures of these. Optionally,
treating can further include (e.g., subsequently to releasing
sugars) utilizing (e.g., by contacting with the sugars and/or
biomass) one or more organisms to produce the hydroxy-carboxylic
acid. For example, the sugars can be fermented by a sugar
fermenting organism to the hydroxyl acid. Sugars that are released
from the biomass can be purified (e.g., prior to fermenting) by,
for example, a method selected from electrodialysis, distillation,
centrifugation, filtration, cation exchange chromatography and
combinations of these in any order.
[0008] In some implementation, converting comprises polymerizing
the lactic acid to a polymer (e.g., polymerizing in a melt such as
without an added solvent). For example, polymerizing methods can be
selected from direct condensation of the lactic acid, azeotropic
dehydrative condensation of the lactic acid, and dimerizing the
lactic acid to lactide followed by ring opening polymerization of
the lactide. The polymerization can be in a melt (e.g., without a
solvent and above the melting point of the polymer) or can be in a
solution (e.g., with an added solvent).
[0009] Optionally, when the polymerization method is direct
condensation, the polymerization can include utilizing coupling
agents and/or chain extenders to increase the molecular weight of
the polymer. For example, the coupling agents and/or chain
extenders can include triphosgene, carbonyl diimidazole,
dicyclohexylcarbodiimide, diisocyanate, acid chlorides, acid
anhydrides, epoxides, thiirane, oxazoline, orthoester, and mixtures
of these. Alternatively, the polymer can have a co monomer which is
a polycarboxylic acid or polyols or a combination of these.
[0010] Optionally, polymerizations can be done utilizing catalysts
and/or promoters. For example, Lewis and Bronsted (protonic) acids
can be used. Examples of the acids include H.sub.3PO.sub.4,
H.sub.2SO.sub.4, methane sulfonic acid, p-toluene sulfonic acid,
NAFION.RTM. NR 50 H+ form From DuPont, Wilmington Del., Acids
supported on polymers, metals, Mg, Al, Ti, Zn, Sn, metal oxides,
TiO.sub.2, ZnO, GeO.sub.2, ZrO.sub.2, SnO.sub.2, Sb.sub.2O.sub.3,
metal halides, ZnCl.sub.2, SnCl.sub.2, SnCl.sub.4, Mn(AcO).sub.2,
Fe.sub.2(LA).sub.3, Co(AcO).sub.2, Ni(AcO).sub.2, Cu(OA).sub.2,
Zn(LA).sub.2, Y(OA).sub.3, Al(i-PrO).sub.3,
Ti(BuO).sub.4, TiO(acac).sub.2, (Bu).sub.2SnO, tin octoate,
solvates of any of these and mixtures of these can be used.
[0011] The polymerizations or at least a portion of the
polymerizations can be done at a temperature between about 100 and
about 200.degree. C., such as between about 110 and about
170.degree. C. or between about 120 and about 160.degree. C.
Optionally at least a portion of the polymerizations can be
performed under vacuum (e.g., between about 0.1 mm Hg to 300 mm
Hg).
[0012] In the implementations wherein the polymerization method
includes dimerizing the lactic acid to lactide followed by ring
opening polymerization of the lactide, the dimerization can include
heating the lactic acid to between 100 and 200.degree. C. under a
vacuum of about 0.1 to about 100 mmHg. Optionally, the dimerization
(e.g., dimerization reaction) can include utilizing a catalyst.
Catalysts can, for example, include Sn octoate, Li carbonate, Zn
diacetate dehydrate, Ti tetraisopropoxide, potassium carbonate, tin
powder and mixtures of these. Optionally, a ring opening
polymerization catalyst is utilized. For example, the ring opening
polymerization catalyst can be chosen from protonic acids, HBr,
HCl, triflic acid, Lewis acids, ZnCl.sub.2, AlCl.sub.3, anions,
potassium benzoate, potassium phenoxide, potassium t-butoxide, and
zinc stearate, metals, Tin, zinc, aluminum, antimony, bismuth,
lanthanide and other heavy metals, Tin (II) oxide and tin (II)
octoate (e.g., 2-ethylhexanoate), tetra phenyl tin, tin (II) and
(IV) halogenides, tin (II) acetylacetonoate, distannoxanes (e.g.,
hexabutyldistannoxane, R.sub.3SnOSnR.sub.3 where R groups are alkyl
or aryl groups), Al(OiPr).sub.3, other functionalized aluminum
alkoxides (e.g., aluminum ethoxide, aluminum methoxide), ethyl
zinc, lead (II) oxide, antimony octoate, bismuth octoate, rare
earth catalysts, yttrium tris(methyl lactate), yttrium
tris(2-N-N-dimethylamino ethoxide), samarium
tris(2-N-N-dimethylamino ethoxide), yttrium tris(trimethylsilyl
methyl), lanthanum tris(2,2,6,6-tetramethylheptanedionate),
lanthanum tris(acetylacetonate), yttrium octoate, yttrium
tris(acetylacetonate), yttrium
tris(2,2,6,6-tetramethylheptanedionate), combinations of these
(e.g., ethyl zinc/aluminum isopropoxide) and mixtures of these.
[0013] In the implementations wherein polymers are made from the
lactic acid, the methods can further include blending the polymer
with a second polymer. For example, a second polymer can include
polyglycols, polyvinyl acetate, polyolefins, styrenic resins,
polyacetals, poly(meth)acrylates, polycarbonate, polybutylene
succinate, elastomers, polyurethanes, natural rubber,
polybutadiene, neoprene, silicone, and combinations of these.
[0014] In other implementations wherein polymers are made from the
lactic acid a co-monomer can be co-polymerized with the lactic acid
or lactide For example, the co-monomer can include elastomeric
units, lactones, glycolic acid, carbonates, morpholinediones,
epoxides, 1,4-benzodioxepin-2,5-(3H)-dione glycosalicylide,
1,4-benzodioxepin-2,5-(3H, 3-methyl)-dione lactosalicylide,
dibenzo-1,5 dioxacin-6-12-dione disalicylide, morpholine-2,5-dione,
1,4-dioxane-2,5-dione glycolide, oxepane-2-one
.epsilon.-caprolactone, 1,3-dioxane-2-one trimethylene carbonate,
2,2-dimethyltrimethylene carbonate, 1,5-dioxepane-2-one,
1,4-dioxane-2-one p-dioxanone, gamma-butyrolactone,
beta-butyrolactone, beta-methyl-delta-valerolactone,
1,4-dioxane-2,3-dione ethylene oxalate, 3-[benzyloxycarbonyl
methyl]-1,4-dioxane-2,5-dione, ethylene oxide, propylene oxide,
5,5'(oxepane-2-one), 2,4,7,9-tetraoxa-spiro[5,5]undecane-3,8-dione,
spiro-bis-dimethylene carbonate and mixtures of these.
[0015] In any implementation wherein polymers are made, the
polymers can be combined with fillers (e.g., by extrusion and/or
compression molding). For example, some fillers that can be used
include silicates, layered silicates, polymer and organically
modified layered silicate, synthetic mica, carbon, carbon fibers,
glass fibers, boric acid, talc, montmorillonite, clay, starch, corn
starch, wheat starch, cellulose fibers, paper, rayon, non-woven
fibers, wood flours, whiskers of potassium titanate, whiskers of
aluminum borate, 4,4'-thiodiphenol, glycerol and mixtures of
these.
[0016] In any implementation wherein polymers are made, the method
can further include branching and/or cross linking the polymer. For
example, the polymers can be treated with a cross linking agent
including 5,5'-bis(oxepane-2-one)(bis-.epsilon.-caprolactone)),
spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide,
benzoyl peroxide, unsaturated alcohols, hydroxyethyl methacrylate,
2-butene-1,4-diol, unsaturated anhydrides, maleic anhydride,
saturated epoxides, glycidyl methacrylate, irradiation and
combinations of these. Optionally, a molecule (e.g., a polymer) can
be grafted to the polymer. For example, grafting can be done
treating the polymer with irradiation, peroxide, crossing agents,
oxidants, heating or any method that can generate a cation, anion
or radical on the polymer.
[0017] In any implementation wherein polymers are processed,
processing can include injection molding, blow molding and
thermoforming.
[0018] In any implementation wherein polymers are processed, the
polymers can be combined with a dye and/or a fragrance. For
example, dyes that can be used include blue 3, blue 356, brown 1,
orange 29, violet 26, violet 93, yellow 42, yellow 54, yellow 82
and combinations of these. Examples of fragrances include wood,
evergreen, redwood, peppermint, cherry, strawberry, peach, lime,
spearmint, cinnamon, anise, basil, bergamot, black pepper, camphor,
chamomile, citronella, eucalyptus, pine, fir, geranium, ginger,
grapefruit, jasmine, juniper berry, lavender, lemon, mandarin,
marjoram, musk, myrrh, orange, patchouli, rose, rosemary, sage,
sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, new
car or mixtures of these fragrances. Fragrances can be used in any
amount, for example, between about 0.005% by weight and about 20%
by weight (e.g., between about 0.1% and about 5 wt. %, between
about 0.25 wt. % and about 2.5%).
[0019] In any implementation wherein polymers are processed, the
polymer can be blended with a plasticizer. For example,
plasticizers include triacetin, tributyl citrate, polyethylene
glycol, GRINDSTED.RTM. SOFT-N-SAFE (from Danisco, DuPont,
Wilmington Del., diethyl bishydroxymethyl malonate) and mixtures of
these.
[0020] In any of the implementations wherein polymers are made, the
polymers can be processed or further processed by shaping, molding,
carving, extruding and/or assembling the polymer into the
product.
[0021] In another aspect, the invention relates to products made by
the methods discussed above. For example, the products include a
converted hydroxy-carboxylic acid wherein the hydroxy-carboxylic
acid is produced by the fermentation of biomass derived sugars
(e.g., glycolic acid, D-lactic acid and/or L-lactic acid, D-malic
acid, L-malic, citric acid and D-tartaric acid, L-tartaric acid and
meso-tartaric acid). The biomass includes cellulosic and
lignocellulosic materials and these can release sugars by acidic or
enzymatic saccharification. In addition, the biomass can be
treated, e.g., by irradiation.
[0022] The products, for example, include polymers, including one
or more hydroxyl acids in the polymer backbone and optionally
non-hydroxy carboxylic acids in the polymer backbone. Optionally
the polymers can be cross-linked or graft co-polymers. Optionally
the polymer can be, blended with a second polymer, blended with a
plasticizer, blended with an elastomer, blended with a fragrance,
blended with a dye, blended with a pigment, blended with a filler
or blended with a combination of these.
[0023] In yet another embodiment, the invention relates to a system
for polymerization including a reaction vessel, a screw extruder
and a condenser. The system also includes a recirculating fluid
flow path from an outlet of the reaction vessel to an inlet of the
screw extruder and from an outlet of the screw extruder to an inlet
to the reaction vessel. In addition, the system includes a fluid
flow path from a second outlet of the reaction vessel to an inlet
of the condenser. Optionally, the system further includes a vacuum
pump in fluid connection with the second fluid flow path for
producing a vacuum in the second fluid flow path. Also optionally,
the system can include a control valve that in a first position
provides a non-disrupted flow in the recirculating fluid flow path
and in a second position provides a second fluid flow path. In some
implementations, the second fluid flow path is from the outlet of
the reaction vessel to an inlet of a pelletizer. In other
implementations, the second fluid flow path is from the outlet of
the reaction vessel to the inlet of the extruder and from the
outlet of the extruder to the inlet of a pelletizer.
[0024] Some of the products described herein, for example, lactic
acid, can be produced by chemical methods. However, fermentative
methods can be much more efficient, providing high biomass
conversion, selective conversion and high production rates. In
particular, fermentative methods can produce D or L isomers of
hydroxy-carboxylic acids (e.g., lactic acid) at chiral purity of
near 100% or mixtures of these isomers, whereas the chemical
methods typically produce racemic mixtures of the D and L isomers.
When a hydroxy-carboxylic acid is listed without its
stereochemistry it is understood that D, L, meso, and/or mixtures
are assumed.
[0025] The methods describe herein are also advantageous in that
the starting materials (e.g., sugars) can be completely derived
from biomass (e.g., cellulosic and lignocellulosic materials). In
addition, some of the products described herein such as polymers of
hydroxy-carboxylic acids (e.g., poly lactic acid) are compostable,
biodegradable and/or recyclable. Therefore, the methods described
herein can provide useful materials and products from renewable
sources (e.g., biomass) wherein the products themselves can be
re-utilized or simply safely returned to the environment.
[0026] For example, some products that can be made by the methods,
systems or equipment described herein include personal care items,
tissues, towels, diapers, green packaging, compostable pots,
consumer electronics, laptop casings, mobile phone casings,
appliances, food packaging, disposable packaging, food containers,
drink bottles, garbage bags, waste compostable bags, mulch films,
controlled release matrices, controlled release containers,
containers for fertilizers, containers for pesticides, containers
for herbicides, containers for nutrients, containers for
pharmaceuticals, containers for flavoring agents, containers for
foods, shopping bags, general purpose film, high heat film, heat
seal layer, surface coating, disposable tableware, plates, cups,
forks, knives, spoons, sporks, bowls, automotive parts, panels,
fabrics, under hood covers, carpet fibers, clothing fibers, fibers
for garments, fibers for sportswear, fibers for footwear, surgical
sutures, implants, scaffolding and drug delivery systems.
[0027] Other features and advantages of the invention will be
apparent from the following detailed description, and from the
claims.
DESCRIPTION OF THE DRAWING
[0028] The foregoing will be apparent from the following more
particular description of example embodiments of the invention, as
illustrated in the accompanying. The drawings are not necessarily
to scale, emphasis instead being placed upon illustrating
embodiments of the present invention.
[0029] FIG. 1 is a flow diagram showing processes for manufacturing
products from a biomass feedstock
[0030] FIG. 2 is a schematic showing some biochemical pathways for
the fermentation of sugars to lactic acid.
[0031] FIG. 3 is a schematic showing some of the possible lactic
acid derived products.
[0032] FIG. 4 is a schematic showing some possible chemical
pathways for producing poly lactic acid.
[0033] FIG. 5 is a schematic view of a reaction system for
polymerizing lactic acid.
[0034] FIG. 6A is a top view of a first embodiment of a
reciprocating scraper. FIG. 6B is a front cut-out view of the first
embodiment of a reciprocating scraper. FIG. 6C is a top view of a
second embodiment of a reciprocating scraper. FIG. 6D is a front
cut-out view of the second embodiment of a reciprocating
scraper.
[0035] FIG. 7 is a plot of lactic acid production in a 1.2 L
Bioreactor.
[0036] FIG. 8 is a plot of lactic acid production in a 20 L
Bioreactor.
[0037] FIG. 9 is a plot of GPC data for poly lactic acid.
[0038] FIG. 10 shows the chemical structures of some exemplary
hydroxyl acids.
DETAILED DESCRIPTION
[0039] Using the equipment, methods and systems described herein,
cellulosic and lignocellulosic feedstock materials, for example,
that can be sourced from biomass (e.g., plant biomass, animal
biomass, paper, and municipal waste biomass) and that are often
readily available but difficult to process, can be turned into
useful products such as sugars and hydroxy-carboxylic acids.
Included are equipment, methods and systems to chemically convert
the primary products produced from the biomass to secondary product
such as polymers (e.g., poly lactic acid) and polymer derivatives
(e.g., composites, elastomers and co-polymers).
[0040] Biomass is a complex feedstock. For example, lignocellulosic
materials include different combinations of cellulose,
hemicellulose and lignin. Cellulose is a linear polymer of glucose.
Hemicellulose is any of several heteropolymers, such as xylan,
glucuronoxylan, arabinoxylan and xyloglucan. The primary sugar
monomer present (e.g., present in the largest concentration) in
hemicellulose is xylose, although other monomers such as mannose,
galactose, rhamnose, arabinose and glucose are present. Although
all lignins show variation in their composition, they have been
described as an amorphous dendritic network polymer of phenyl
propene units. The amounts of cellulose, hemicellulose and lignin
in a specific biomass material depend on the source of the biomass
material. For example, wood-derived biomass can be about 38-49%
cellulose, 7-26% hemicellulose and 23-34% lignin depending on the
type. Grasses typically are 33-38% cellulose, 24-32% hemicellulose
and 17-22% lignin. Clearly lignocellulosic biomass constitutes a
large class of substrates.
[0041] Enzymes and biomass-destroying organisms that break down
biomass, such as the cellulose, hemicellulose and/or the lignin
portions of the biomass as described above, contain or manufacture
various cellulolytic enzymes (cellulases), ligninases, xylanases,
hemicellulases or various small molecule biomass-destroying
metabolites. A cellulosic substrate is initially hydrolyzed by
endoglucanases at random locations producing oligomeric
intermediates. These intermediates are then substrates for
exo-splitting glucanases such as cellobiohydrolase to produce
cellobiose from the ends of the cellulose polymer. Cellobiose is a
water-soluble 1,4-linked dimer of glucose. Finally, cellobiase
cleaves cellobiose to yield glucose. In the case of hemicellulose,
a xylanase (e.g., hemicellulase) acts on this biopolymer and
releases xylose as one of the possible products.
[0042] FIG. 1 is a flow diagram showing processes for manufacturing
is a flow diagram showing processes for manufacturing
hydroxy-carboxylic acids from a feedstock (e.g., cellulosic or
lignocellulosic materials). In an initial step (110) the method
includes optionally mechanically treating a cellulosic and/or
lignocellulosic feedstock, for example, to comminute/size reduce
the feedstock. Before and/or after this treatment, the feedstock
can be treated with another physical treatment (112), for example,
irradiation, sonication, steam explosion, oxidation, pyrolysis or
combinations of these, to reduce or further reduce its
recalcitrance. A sugar solution e.g., including glucose and/or
xylose, is formed by saccharifying the feedstock (114). The
saccharification can be, for example, accomplished efficiently by
the addition of one or more enzymes, e.g., cellulases and/or
xylanases (111) and/or one or more acids. A product or several
products can be derived from the sugar solution, for example, by
fermentation to a hydroxy-carboxylic acid (116). Following
fermentation, the fermentation product (e.g., or products, or a
subset of the fermentation products) can be purified or they can be
further processed, for example, polymerized and/or isolated (124).
Optionally, the sugar solution is a mixture of sugars and the
organism selectively ferments only one of the sugars. The
fermentation of only one of the sugars in a mixture can be
advantageous as described in International App. No.
PCT/US2014/021813 filed Mar. 7, 2014, the entire disclosure of
which is incorporated herein by reference. If desired, the steps of
measuring lignin content (118) and setting or adjusting process
parameters based on this measurement (120) can be performed at
various stages of the process, for example, as described in U.S.
Pat. No. 8,415,122, issued Apr. 9, 2013 the entire disclosure of
which is incorporated herein by reference. Optionally, enzymes
(e.g., in addition to cellulases and xylanases) can be added in
step (114), for example, a glucose isomerase can be used to
isomerize glucose to fructose. Some relevant uses of isomerase are
discussed in PCT Application No. PCT/US12/71093, filed on Dec. 20,
2012, published as WO 2013/096700 the entire disclosure of which is
incorporated herein by reference.
[0043] In some embodiments the liquids after saccharification
and/or fermentation can be treated to remove solids, for example,
by centrifugation, filtration, screening, or rotary vacuum
filtration. For example, some methods and equipment that can be
used during or after saccharification are disclosed in
International App. No. PCT/US2013/048963 filed Jul. 1, 2013, and
International App. No. PCT/US2014/021584, filed on Mar. 7, 2014,
the entire disclosures of which are incorporated herein by
reference. In addition other separation techniques can be used on
the liquids, for example, to remove ions and de-colorize. For
example, chromatography, simulated moving bed chromatograph and
electrodialysis can be used to purify any of the solutions and/or
suspensions described herein. Some of these methods are discussed
in International App. No. PCT/US2014/021638, filed on Mar. 7, 2014,
and International App. No. PCT/US2014/021815, filed on Mar. 7,
2014, the entire disclosures of which are incorporated herein by
reference. Solids that are removed during the processing can be
utilized for energy co-generation, for example, as discussed in
International App. No. PCT/US2014/021634, filed on Mar. 7, 2014,
the entire disclosure of which is herein incorporated by
reference.
[0044] Optionally, the sugars released from biomass as described in
FIG. 1, for example, glucose, xylose, sucrose, maltose, lactose,
mannose, galactose, arabinose, homodimers and heterodimers of these
(e.g., cellobiose, sucrose), trimers, oligomers and mixtures of
these, can be fermented to hydroxy-carboxylic acids such as alpha,
beta or gamma hydroxyl acids (e.g., lactic acid). In some
embodiments, the saccharification and fermentation are done
simultaneously, for example, using the thermophilic organism such
as Bacillus coagulans MXL-9 as described by S. L. Walton in J. Ind.
Microbiol. Biotechnol. (2012) pg. 823-830.
[0045] Hydroxy-carboxylic acids that can be produced by the methods
systems and equipment described herein include, for example, of
alpha, beta, gamma, and delta hydroxy-carboxylic acids. FIG. 10
shows the chemical structures of some hydroxyl acids. That is, if
there is only one hydroxyl group it can be at any of the alpha,
beta, gamma or delta carbon atoms in the carbon chain. The carbon
chain may be a straight chain, branched or cyclic system. The
hydroxy carboxylic acid may also include fatty acids of carbon
chain lengths of 10 to 22 with the hydroxy substituent at the
alpha, beta, gamma, or delta carbon.
[0046] The hydroxy-carboxylic acids include those with multiple
hydroxy substituents, or in alternative description a poly hydroxy
substituted carboxylic acid. Such hydroxy-carboxylic acids can be
poly-hydroxy-carboxylic acid, e.g. di-, tri-, tetra-, penta-,
hexa-hepta- and octa-hydroxy substituted carboxylic acid. The
carbon chain of the carboxylic acid may be straight chained,
branched, cyclic, or alicyclic. Examples of this are tartaric acid
and its isomers, dihydroxy-3-methylpentanoic acid,
3,4-dihydroxymandelic acid, gluconic acid, glucuronic acid and the
like.
[0047] For example, the hydroxy-carboxylic acids include glycolic
acid, lactic acid (e.g., D, L or mixtures of D and L), malic acid,
citric acid, tartaric acid, carmine, cyclobutyrol, 3-dehydroquinic
acid, diethyl tartrate, 2,3-dihydroxy-3-methylpentanoic acid,
3,4-dihydroxymandelic acid, glyceric acid, homocitric acid,
homoisocitric acid, beta-hydroxy beta-methylbutyric acid,
4-hydroxy-4-methylpentanoic acid, hydroxybutyric acid,
2-hydroxybutyric acid, beta-hydroxybutyric acid,
gamma-hydroxybutyric acid, alpha-hydroxyglutaric acid,
5-hydroxyindoleacetic acid, 3-hydroxyisobutyric acid,
3-hydroxypentanoic acid, 3-hydroxypropionic acid, hydroxypyruvic
acid, gluconic acid, glucuronic acid, alpha, beta, gamma or
delta-hydroxyvaleric acid; isocitric acid, isopropylmalic acid,
kynurenic acid, mandelic acid, mevalonic acid, monatin, myriocin,
pamoic acid, pantoic acid, prephenic acid, shikimic acid, tartronic
acid, threonic acid, tropic acid, vanillylmandelic acid,
xanthurenic acid and mixtures of these. For those
hydroxy-carboxylic acids listed all of the stereo isomers are
included in the list. For instance, tartaric acid includes, the D,
L, and meso isomers and mixtures thereof.
Preparation of Lactic Acid
[0048] Organisms can utilize a variety of metabolic pathways to
convert the sugars to lactic acid, and some organisms selectively
only can use specific pathways. Some organisms are homofermentative
while others are heterofermentative. For example, some pathways are
shown in FIG. 2 and are described in Journal of Biotechnology 156
(2011) 286-301. The pathway typically utilized by organisms
fermenting glucose is the glycolytic pathway 2. Five carbon sugars,
such as xylose, can utilize the heterofermentative phosphoketolase
(PK) pathway. The PK pathway converts two of the 5 carbons in
xylose to acetic acid on the remaining 3 to lactic acid (through
pyruvate). Another possible pathway for five carbon sugars is the
pentose phosphate (PP)/glycolytic pathway that only produces lactic
acid.
[0049] Several organisms can be utilized to ferment the biomass
derived sugars to lactic acid. The organisms can be, for example,
lactic acid bacteria and fungi. Some specific examples include
Rhizopus arrhizus, Rhizopus oryzae, (e.g., NRRL-395, ATCC 52311,
NRRL 395, CBS 147.22, CBS 128.08, CBS 539.80, CBS 328.47, CBS
127.08, CBS 321.35, CBS 396.95, CBS 112.07, CBS 127.08, CBS
264.28), Enterococcus faecalis (e.g. RKY1), Lactobacillus rhamnosus
(e.g. ATCC 10863. ATCC 7469, CECT-288, NRRL B-445), Lactobacillus
helveticus (e.g. ATCC 15009, R211), Lactobacillus bulgaricus (e.g.
NRRL B-548, ATCC 8001, PTCC 1332), Lactobacillus casei (e.g. NRRL
B-441), Lactobacillus plantarum (e.g. ATCC 21028, TISTR No. 543,
NCIMB 8826), Lactobacillus pentosus (e.g. ATCC 8041), Lactobacillus
amylophilus (e.g. GV6), Lactobacillus delbrueckii (e.g. NCIMB 8130,
TISTR No. 326, Uc-3, NRRL-B445, IFO 3202, ATCC 9649), Lactococcus
lactis ssp. lactis (e.g. IFO 12007), Lactobacillus paracasei No. 8,
Lactobacillus amylovorus (ATCC 33620), Lactobacillus sp. (e.g.
RKY2), Lactobacillus coryniformis ssp. torquens (e.g. ATCC 25600,
B-4390), Rhizopus sp. (e.g. MK-96-4196), Enterococcus
casseliflavus, Lactococcus lactis (TISTR No. 1401), Lactobacillus
casei (TISTR No. 390), Lactobacillus thermophiles, Bacillus
coagulans (e.g., MXL-9, 36D1, P4-102B), Enterococcus mundtii (e.g.,
QU 25), Lactobacillus delbrueckii, Acremonium cellulose,
Lactobacillus bifermentans, Corynebacterium glutamicum, L.
acetotolerans, L. acidifarinae, L. acidipiscis, L. acidophilus, L.
agilis, L. algidus, L. alimentarius, L. amylolyticus, L.
amylophilus, L. amylotrophicus, L. amylovorus, L. animalis, L.
antri, L. apodemi, L. aviarius, L. bifermentans, L. brevis (e.g.,
B-4527), L. buchneri, L. camelliae, L. casei, L. catenaformis, L.
ceti, L. coleohominis, L. collinoides, L. composti, L. concavus, L.
coryniformis, L. crispatus, L. crustorum, L. curvatus, L.
delbrueckii subsp. Delbrieckii (e.g., NRRL B-763, ATCC 9649), L.
delbrueckii subsp. bulgaricus, L. delbrueckii subsp. lactis (e.g.,
B-4525), L. dextrinicus, L. diolivorans, L. equi, L. equigenerosi,
L. farraginis, L. farciminis, L. fermentum, L. fornicalis, L.
fructivorans, L. frumenti, L. fuchuensis, L. gallinarum, L.
gasseri, L. gastricus, L. ghanensis, L. graminis, L. hammesii, L.
hamsteri, L. harbinensis, L. hayakitensis, L. helveticus, L.
hilgardii, L. homohiochii, L. iners, L. ingluviei, L. intestinalis,
L. jensenii, L. johnsonii, L. kalixensis, L. kefiranofaciens, L.
kefiri, L. kimchii, L. kitasatonis, L. kunkeei, L. leichmannii, L.
lindneri, L. malefermentans, L. mali, L. manihotivorans, L.
mindensis, L. mucosae, L. murinus, L. nagelii, L. namurensis, L.
nantensis, L. oligofermentans, L. oris, L. panis, L. pantheris, L.
parabrevis, L. parabuchneri, L. paracollinoides, L. parafarraginis,
L. parakefiri, L. paralimentarius, L. paraplantarum, L. pentosus,
L. perolens, L. plantarum (e.g., ATCC 8014), L. pontis, L.
psittaci, L. rennini, L. reuteri, L. rhamnosus, L. rimae, L.
rogosae, L. rossiae, L. ruminis, L. saerimneri, L. sakei, L.
salivarius, L. sanfranciscensis, L. satsumensis, L. secaliphilus,
L. sharpeae, L. siliginis, L. spicheri, L. suebicus, L.
thailandensis, L. ultunensis, L. vaccinostercus, L. vaginalis, L.
versmoldensis, L. vini, L. vitulinus, L. zeae, L. zymae, and
Pediococcus pentosaceus (ATCC 25745).
[0050] Alternatively, the microorganism used for converting sugars
to hydroxy-carboxylic acids, including lactic acid, Lactobacillus
casei, Lactobacillus rhamnosus, Lactobacillus delbrueckii
subspecies delbrueckii, Lactobacillus plantarum, Lactobacillus
coryniformis subspecies torquens, Lactobacillus pentosus,
Lactobacillus brevis, Pediococcus pentosaceus, Rhizopus oryzae,
Enterococcus faecalis, Lactobacillus helveticus, Lactobacillus
bulgaricus, Lactobacillus casei, lactobacillus amylophilus and
mixtures thereof.
[0051] Using the methods, equipment and systems described herein,
either D or L isomers of lactic acid at an optical purity of near
100% (e.g., at least about 80%, at least about 85%, at least about
90%, at least about 95%, at least about 99%) can be produced.
Optionally, mixtures of the isomers can be produced in any ratio,
for example, from 0% optical purity of any isomer up to 100%
optical purity of any isomer. For example, the species
Lactobacillus delbrueckii (NRRL-B445) is reported to produce a
mixture of D and L isomers, Lactobacillus rhamnosus (CECT-28) is
reported to produce the L isomer while Lactobacillus delbrueckii
(IF 3202) is reported to produce the D isomer (Wang et al. in
Bioresource Technology, June, 2010). As a further example,
organisms that predominantly produce the L(+)-isomer are L.
amylophilus, L. bavaricus, L. casei, L. maltaromicus and L.
salivarius, while L. delbrueckii, L. jensenii and L. acidophilus
produce the D(-)-isomer or mixtures of both.
[0052] Genetically modified organisms can also be utilized. For
example, genetically modified organisms (e.g., lactobacillus,
Escherichia coli) that are modified to express either L-Lactate
dehydrogenase or D-lactate dehydrogenase to produce more L-Lactic
acid or D-Lactic acid, respectively. In addition, some yeasts and
Escherichia coli have been genetically modified to produce lactic
acid from glucose and/or xylose.
[0053] Co-cultures of organisms, for example, chosen from organisms
as described herein, can be used in the fermentations of sugars to
hydroxy-carboxylic acid in any combination. For example, two or
more bacteria, yeasts and/or fungi can be combined with one or more
sugars (e.g., glucose and/or xylose) where the organisms ferment
the sugars together, selectively and/or sequentially. Optionally,
one organism can be added first and the fermentation proceed for a
time, for example, until it stops fermenting one or more of the
sugars, and then a second organism can be added to further ferment
the same sugar or ferment a different sugar. Co-cultures can also
be utilized, for example, to tune in a desirable racemic mixture of
D and L lactic acid by combining a D-fermenting and L-fermenting
organism in an appropriate ratio to form the targeted racemic
mixture.
[0054] In some embodiments, fermentations utilize Lactobacillus.
For example, the fermentation of biomass derived glucose by
Lactobacillus can be very efficient (e.g., fast, selective and with
high conversion). In other embodiments the production of lactic
acid uses filamentous fungi. For example, Rhizopus species can
ferment glucose aerobically to lactic acid. In addition, some fungi
(e.g. R. oryzae and R. arrhizus) produce amylases so that the
direct fermentation of starches can accomplished without adding
external amylases. Finally some fungi (e.g., R. oryzae) can ferment
xylose as well as glucose where most lactobacillus are not
efficient in fermenting pentose sugars.
[0055] In some embodiments some additives (e.g., media components)
can be added during the fermentation. For example, additives that
can be utilized include yeast extract, rice bran, wheat bran, corn
steep liquor, black strap molasses, casein hydrolyzate, vegetable
extracts, corn steep solid, ram horn waste, peptides, peptone
(e.g., bacto-peptone, polypeptone), pharmamedia, flower (e.g.,
wheat flour, soybean flour, cottonseed flour), malt extract, beef
extract, tryptone, K.sub.2HPO.sub.4, KH.sub.2PO.sub.4,
Na.sub.2HPO.sub.4, NaH.sub.2PO.sub.4, (NH.sub.4).sub.2PO.sub.4,
NH.sub.4OH, NH.sub.4NO, urea ammonium citrate, nitrilotriacetic
acid, MnSO.sub.4.5H.sub.2O, MgSO.sub.4.7H.sub.2O, CaCl.sub.2.
2H.sub.2O, FeSO.sub.4.7H.sub.2O, B-vitamins (e.g., thiamine,
riboflavin, niacin, niacinamide, pantothenic acid, pyridoxine,
pyridoxal, pyridoxamine, pyridoxine hydrochloride, biotin, folic
acid), amino acids, sodium-L-glutamate, Na.sub.2EDTA, sodium
acetate, ZnSO.sub.4.7H.sub.2O, ammonium molybdate tetrahydrate,
CuCl.sub.2, CoCl.sub.2 and CaCO.sub.3. Addition of protease can
also be beneficial during the fermentation. Optionally, surfactants
such as TWEEN.TM. 80 and antibiotics such as chloramphenicol can
also be beneficial. Additional carbon sources, for example,
glucose, xylose and other sugars. Antifoaming compounds such as
Antifoam 204 can also be utilized.
[0056] In some embodiments the fermentation can take from about 8
hours to several days. For example, some batch fermentations can
take from about 1 to about 20 days (e.g., about 1-10 days, about
3-6 days, about 8 hours to 48 hours, about 8 hours to 24
hours).
[0057] In some embodiments the temperature during the fermentation
is controlled. For example, the temperature can be controlled
between about 20.degree. C. and 50.degree. C. (e.g., between about
25 and 40.degree. C., between about 30 and 40.degree. C., between
about 35 and 40.degree. C.). In some cases, thermophilic organisms
are utilized that operate efficiently above about 50.degree. C.,
for example, between about 50.degree. C. and 100.degree. C. (e.g.,
between about 50-90.degree. C., between about 50 to 80.degree. C.,
between about 50 to 70.degree. C.).
[0058] In some embodiments the pH is controlled, for example, by
the addition of an acid or a base. The pH can be optionally
controlled to be close to neutral (e.g., between about 4-8, between
about 5-7, between about 5-6). Acids, for example, can be protic
acids such as sulfuric, phosphoric, nitric, hydrochloride and
acetic acids. Bases, for example, can include metal hydroxides
(e.g., sodium and potassium hydroxide), ammonium hydroxide, and
calcium carbonate. Phosphate and other buffers can also be
utilized.
[0059] Fermentation methods include, for example, batch, fed batch,
repeated batch or continuous reactors. Often batch methods can
produce higher concentrations of lactic acids, while continuous
methods can lead to higher productivities.
[0060] Fed batch methods can include adding media components and
substrate (e.g., sugars from biomass) as they are depleted.
Optionally, products, intermediates, side products and/or waste
products, can be removed as they are produced. In addition, solvent
(e.g., water) can be added or removed to maintain the optimal
amount for the fermentation.
[0061] Options include cell-recycling. For example, using a hollow
fiber membrane to separate cells from media components and products
after fermentation is complete. The cells can then be re-utilized
in repeated batches. In other optional methods, the cells can be
supported, for example, as described in U.S. application Ser. No.
13/293,971, filed on Nov. 10, 2011 and U.S. Pat. No. 8,377,668,
issued Feb. 19, 2013, the entire disclosures of which are herein
incorporated by reference.
[0062] The fermentation broth can be neutralized using calcium
carbonate or calcium hydroxide which can form calcium lactate.
Calcium lactate is soluble in water (e.g., about 7.9 g/100 mL). The
calcium lactate broth can then be filtered to remove cells and
other insoluble materials. In addition the broth can be treated
with a decolorizing agent. For example, the broth can be filtered
through carbon. The broth is then concentrated, e.g., by
evaporation of the water optionally under vacuum and/or mild
heating, and can be crystallized or precipitated. Acidification,
for example, with sulfuric acid, releases the lactic acid back into
solution which can be separated (e.g., filtered) from the insoluble
calcium salts, e.g., calcium sulfate. Addition of calcium carbonate
during the fermentation can also serve as a way to reduce product
inhibition since the calcium lactate is not inhibitory or causes
less product inhibition.
[0063] Optionally, reactive distillation can also be used to purify
D-lactic acid and/or L-lactic acid. For example, methylation of
D-lactic acid and/or L-lactic acid provides the methyl ester which
can be distillated to pure ester which can then be hydrolyzed to
the acid and methanol that can be recycled. Esterification to other
esters can also be used to facilitate the separation. For example,
reactions with alcohols to the ethyl, propyl, butyl, hexyl, octyl
or even esters with more than eight carbons can be formed and then
extracted in a solvent or distilled.
[0064] Other alternative D-lactic acid and/or L-lactic acid
separation technologies include adsorption, for example, on
activated carbon, polyvinylpyridine, zeolite molecular sieves and
ion exchange resins such as basic resins. Other methods include
ultrafiltration and electrodialysis.
[0065] Precipitation or crystallization of calcium lactate by the
addition of organic solvents is another method for purification.
For example, alcohols (e.g., ethanol, propanol, butanol, hexanol),
ketones (e.g., acetone) can be utilized for this purpose.
[0066] Similar methods can be utilized for the preparation of other
hydroxy-carboxylic acids. For example, the fermentative methods and
procedures can be applicable for any of the hydroxy-carboxylic
acids described herein.
Lactic Acid Uses
[0067] Lactic acid produced as described herein can be used, for
example, in the food industry as a preservative, acidulant and
flavoring agent. Lactic acid can be used in a wide range of food
applications such as bakery products, beverages, meat products,
confectionery, dairy products, salads, dressings, ready meals.
Lactic acid in food products usually serves either as a pH
regulator or as a preservative. It is can also be used as a
flavoring agent, for example, imparting a sour taste to foods.
Lactic acid can be used in meat, poultry and fish, for example, in
the form of sodium or potassium lactate to extend shelf life,
control pathogenic bacteria (e.g., improving food safety), enhance
and protect meat flavor, improve water binding capacity and reduce
sodium. Lactic acid is also used as an acidity regulator in
beverages such as soft drinks and fruit juices. Lactic acid is
effective in preventing the spoilage of olives, gherkins, pearl
onions and other vegetables preserved in brine. Lactic acid can
also be used as a preservative and/or flavoring additive in salads
and dressings. Lactic acid is also used in formulating hard-boiled
candy, fruit gums and other confectionery products. Lactic acid is
used as an acidification agent for many dairy products for example,
yogurts and cheeses. Lactic acid is a natural sourdough acid, and
therefore, it can be used for direct acidification in the
production of sourdough. Lactic acid is used to enhance a broad
range of savory flavors, for example, in meat and dairy
products.
[0068] Calcium lactate as produced by the methods described herein
can also be added to sugar-free foods to prevent tooth decay. For
example, in combinations with chewing gum containing xylitol, it
increases the remineralization of tooth enamel. Calcium lactate is
also added to fresh-cut fruits such as cantaloupes to extend their
shelf life.
[0069] The biomass derived lactic acid as described herein can be
used in pharmaceutical applications, for example, for
pH-regulation, metal sequestration, as a chiral intermediate and as
a natural body constituent in pharmaceutical products. Calcium
lactate is commonly used as an antacid and also as a calcium
supplement. Other salts of lactic acid, for example, salts
containing Mg, Zn and Fe, can also be used as mineral supplements
and fortifying agents.
[0070] Lactic acid as produced by the methods described herein can
also be used in cleaning products. Lactic acid has descaling
properties and is widely applied in household cleaning products.
Also, lactic acid is used as a natural anti-bacterial agent in
disinfecting products.
[0071] The lactic acid produced by the methods described herein can
be used in a wide variety of industrial processes where acidity is
required and where its properties offer specific benefits. Examples
are the manufacture of leather and textile products and computer
disks, as well as car coatings.
[0072] The lactic acid as produced by the methods described herein
can also be utilized as nutrient for animal feed. The lactic acid
can have health promoting properties, thus enhancing the
performance of farm animals. The lactic acid can be also used as an
additive in food and/or drinking water both for animals and
humans.
Products Derived from Lactic Acid
[0073] Lactic acid can be used as a platform chemical for many
industrially relevant chemicals and products. For example, with
reference to FIG. 2, lactic acid can be converted to, lactate
esters such as ethyl lactate, acrylic acid, 1,2-propanediol,
2,3-pentanedione, acetaldehyde, propanoic acid and poly lactic
acid.
[0074] 1,2-propane diol (propylene glycol) can be used as a solvent
and anti-freeze substitute for 1,2-propane diol. Propylene glycol
is also used for de-icing solutions (e.g., airplane de-icing).
Propylene glycol is approved for use as a food additive and can be
used in food industry as a humectant, preservative, lubricant
(e.g., for food processing equipment), solvent (e.g., for
pharmaceutical preparations), plasticizer (e.g., for materials that
come into contact with food).
[0075] Ethyl lactate has uses in pharmaceutical preparations, food
additives, fragrances and as a fine chemical, consumer product
(e.g., cosmetics) and industrial solvent.
[0076] Acetaldehyde is currently produced in a large scale,
primarily from petroleum sources. It is a synthon in a myriad of
organic reactions to produce, for example, ethyl acetate (an
important solvent), perfumes, polyester resins and basic dyes. It
also finds uses as a solvent (e.g., in the rubber, tanning and
paper industries), as a preservative (e.g., fruit and meat), a
flavoring agent and a denaturant for fuel compositions.
[0077] 2,3-pentanedione is useful as a solvent for cellulose
acetate, paints, inks, lacquers. It is also a starting material for
the synthesis of dyes, pesticides and drugs. It also can be used as
a constituent in synthetic flavoring agents.
[0078] (Meth)acrylic acid and its esters (e.g., methyl, butyl,
ethyl, hydroxyethyl and 2-ethylhexyl esters) polymerize through
their double bond to form poly acrylates (e.g., polyacrylic acid).
In addition, acrylic acid and its esters can copolymerize with
other monomers e.g., acrylamides, acrylonitriles, styrene, vinyl
and butadiene) forming copolymers which are used in manufacturing
plastics, coatings, adhesives, elastomers, floor polishes and
paints.
[0079] Propanoic acid can be used as a fungicide and bactericide,
for treatment of grains, hay, poultry litter, drinking water for
animals as well as for the treatment of areas used for storage of
feed materials. It is also a synthon for production of other
chemicals, for example, herbicides and various esters.
[0080] Poly lactic acid is an important biodegradable/recyclable
polymer that will be discussed in detail below.
Polymerization of Lactic Acid
[0081] Lactic acid prepared as described herein can undergo ester
condensation to form dimers (e.g., linear and lactide), trimers,
oligomers and polymers. Polylactic acid (PLA) is therefore, a
polyester of condensed lactic acid. PLA can be further processed
(e.g., grafted, treated, or copolymerized to form side chains
including ionizable groups). Another name for PLA is polylactide.
Both isomers of PLA can form polymers and/or they can be
copolymerized. The properties of the polymer depend strongly on the
amounts of the D and L lactic acid incorporated in the structure,
as will be discussed further on.
[0082] FIG. 4 shows methods for the production of PLA including:
direct condensation combined with chain coupling; azeotropic
dehydrative coupling; and condensation followed by lactide
formation and ring opening polymerization of the lactide.
[0083] A low molecular weight PLA can be produced catalyst free by
the direct self-condensation of lactic acid. This method produces
low molecular weight polymers (e.g., about 1000 to 10,000 Mw, more
typically about 1000 to 5,000). The condensation produces water
which can prevent the production of high molecular weight PLA since
the ester condensation reaction is reversible. In addition, lactide
can be produced by backbiting from a chain end to form the lactide
ring which reduces the molecular weight of the linear polymer.
Therefore, the polycondensation system of PLA involves two
equilibrium reactions; the dehydration/hydrolysis equilibrium for
esterification/de-esterification; and the ring/chain equilibrium
involving the depolymerization of PLA into lactide or
polymerization of the ring to linear polymer.
[0084] One method for production of high molecular weight PLA is by
coupling low Mw PLA, for example, made as described above, using
chain coupling agents. For example, hydroxyl-terminated PLA can be
synthesized by the condensation of lactic acid in the presence of
small amounts of multifunctional hydroxyl compounds such as,
ethylene glycol, propylene glycol, 1,3-propanediol,
1,2-cyclohexanediol, 2-butene-1,4-diol, glycerol, 1,4-butanediol,
1,6-hexanediol. Alternatively, carboxyl-terminated PLA can be
achieved by the condensation of lactic acid in the presence of
small amounts of multifunctional carboxylic acids such as maleic,
succinic, adipic, itaconic and malonic acid. Other chain extending
agents can have heterofunctional groups that couple either on the
carboxylic acid end group of the PLA or the hydroxyl end group, for
example, 6-hydroxycapric acid, mandelic acid, 4-hydroxybenzoic
acid, 4-acetoxybenzoic acid.
[0085] Esterification promotion agents can also be combined with
lactic acid to increase the molecular weight of PLA. For example,
ester promotion agents include phosgene, diphosgene, triphosgene
dicyclohexylcarbodiimide and carbonyldiimidazole. Some potentially
undesirable side products can be produced by this method adding
purification steps to the process. After final purification, the
product can be very clean, free of catalysts and low molecular
weight impurities.
[0086] The polymer molecular weights can also be increase by the
addition of chain extending agents such as isocyanates, acid
chlorides, anhydrides, epoxides, thiirane and oxazoline and
orthoester.
[0087] Azeotropic condensation polymerization is another method to
obtain high molecular weight polymer and does not require chain
extenders or coupling agents. A general procedure for this route
consists of reduced pressure (between 0.1-300 mm Hg) refluxing of
lactic acid for 1-10 hours between 110.degree. C.-160.degree. C. to
remove majority of the condensation water. Catalyst and/or solvents
are added and heated further for 1-10 hours between 110.degree.
C.-180.degree. C. under 0.1-300 mm Hg. The polymer is then isolated
or dissolved (methylene chloride, chloroform) and precipitated by
the addition of a solvent (e.g., methyl ether, diethyl ether,
methanol, ethanol, isopropanol, ethyl acetate, toluene) for further
purification. Solvents used during to polymerization, catalyst,
reaction time, temperature and level of impurities effect the rate
of polymerization and hence the final molecular weight.
[0088] Additives, catalysts and promoters that can optionally be
used include Lewis and Bronsted (protonic) acids such as
H.sub.3PO.sub.4, H.sub.2SO.sub.4, methane sulfonic acid, p-toluene
sulfonic acid, NAFION.RTM. NR 50 H+ form From DuPont, Wilmington
Del., metal catalysts, for example, include Mg, Al, Ti, Zn, Sn.
Some metal oxides that can optionally catalyze the reaction include
TiO.sub.2, ZnO, GeO.sub.2, ZrO.sub.2, SnO, SnO.sub.2,
Sb.sub.2O.sub.3. Metal halides, for example, that can be beneficial
include ZnCl.sub.2, SnCl.sub.2, SnCl.sub.4. Other metal containing
catalysts that can optionally be used include Mn(AcO).sub.2,
Fe.sub.2(LA).sub.3, Co(AcO).sub.2, Ni(AcO).sub.2, Cu(OA).sub.2,
Zn(LA).sub.2, Y(OA).sub.3, Al(i-PrO).sub.3, Ti(BuO).sub.4,
TiO(acac).sub.2, (Bu).sub.2SnO. Combinations and mixtures of the
above catalysts can also be used. For example, two or more
catalysts can be added at one time or sequentially as the
polymerization progresses. The catalysts can also be removed,
replenished and/or regenerated during the course of the
polymerization are for repeated polymerizations. Optional
combinations include protonic acids and one of the metal continuing
catalysts, for example, SnCl.sub.2/p-toluenesulfonic acid.
[0089] The azeotropic condensation can be done partially or
entirely using a solvent. For example, a high boiling and aprotic
solvent such as diphenyl ether, p-xylene, o-chlorotoluene,
o-dichlorobenzene and/or isomers of these. The polymerization can
also be done entirely or partially using melt polycondensation.
Melt polycondensations are done above the melting point of the
polymers/oligomers without organic solvents. For example, at the
beginning of the polymerization when there is a high concentration
of low molecular weight species (e.g., lactic acid and oligomers)
there can be less need for a solvent, while as the molecular weight
of the polymers increases, the addition of a high boiling solvent
can improve the reaction rates.
[0090] During the polymerization, for example, especially at the
beginning of the polymerization when the concentration of lactic
acid is high and water is being formed at a high rate, the lactic
acid/water azeotropic mixture can be condensed and made to pass
through molecular sieves to dehydrate the lactic acid which is then
returned to the reaction vessel.
[0091] Copolymers can be produced by adding monomers other than
lactic acid during the azeotropic condensation reaction. For
example, any of the multifunctional hydroxyl, carboxylic compounds
or the heterofunctional compounds that can be used as coupling
agents for low molecular weight PLA can also be used as co-monomers
in the azeotropic condensation reaction.
[0092] Optionally, ring opening polymerization of lactide can
provide PLA. Lactide can be produced by the depolymerization of low
molecular weight PLA under reduced pressure. The depolymerization
to form the lactide monomers, for example, the D, L and meso forms,
depends on the stereochemistry of the starting lactic acid and
conditions of formation. Methods to form the lactide include
condensing lactic acid, with or without catalysts at
110-180.degree. C. and removing the water of condensation under
vacuum (1 mm Hg-100 mm Hg) to produce 1000-5000 molecular weight
polymer or prepolymer. The prepolymer can then be heated, for
example, to temperatures of about 150-250.degree. C. and at 0.1-100
mmHg to form and distill off the crude lactic acid. The crude
lactic acid can be recrystallized, for example, from a solution of
dry toluene or ethyl acetate.
[0093] Catalysts can be used for lactide formation. For example,
catalysts that can be used include, tin oxide (SnO), Sn(II)
octoate, Li carbonate, Zinc diacetate dehydrate, Ti
tetraisopropoxide, potassium carbonate, tin powder, combinations
thereof and mixtures of these. Catalysts can be used in combination
and/or sequentially.
[0094] The lactide monomer can be ring open polymerized (ROP) by
solution, bulk, melt and suspension polymerization and is catalyzed
by cationic, anionic, coordination or free radical polymerization.
Some catalysts used, for example, include protonic acids, HBr, HCl,
triflic acid, Lewis acids, ZnCl.sub.2, AlCl.sub.3, anions,
potassium benzoate, potassium phenoxide, potassium t-butoxide, and
zinc stearate, metals, Tin, zinc, aluminum, antimony, bismuth,
lanthanide and other heavy metals, Tin (II) oxide and tin (II)
octoate (e.g., 2-ethylhexanoate), tetraphenyl tin, tin (II) and
(IV) halogenides, tin (II) acetylacetonoate, distannoxanes (e.g.,
hexabutyldistannoxane, R.sub.3SnOSnR.sub.3 where R groups are alkyl
or aryl groups), Al(OiPr).sub.3, other functionalized aluminum
alkoxides (e.g., aluminum ethoxide, aluminum methoxide), ethyl
zinc, lead (II) oxide, antimony octoate, bismuth octoate, rare
earth catalysts, yttrium tris(methyl lactate), yttrium
tris(2-N-N-dimethylamino ethoxide), samarium
tris(2-N-N-dimethylamino ethoxide), yttrium tris(trimethylsilyl
methyl), lanthanum tris(2,2,6,6-tetramethylheptanedionate),
lanthanum tris(acetylacetonate), yttrium octoate, yttrium
tris(acetylacetonate), yttrium
tris(2,2,6,6-tetramethylheptanedionate), combinations of these
(e.g., ethyl zinc/aluminum isopropoxide) and mixtures of these.
[0095] In addition to homopolymer, copolymerization with other
cyclic monomers and non-cyclic monomers such as glycolide,
caprolactone, valerolactone, dioxypenone, trimethyl carbonate,
1,4-benzodioxepin-2,5-(3H)-dione glycosalicylide,
1,4-benzodioxepin-2,5-(3H, 3-methyl)-dione Lactosalicylide,
dibenzo-1,5 dioxacin-6-12-dione disalicylide, morpholine-2,5-dione,
1,4-dioxane-2,5-dione glycolide, oxepane-2-one
.epsilon.-caprolactone, 1,3-dioxane-2-one trimethylene carconate,
2,2-dimethyltrimethylene carbonate, 1,5-dioxepane-2-one,
1,4-dioxane-2-one p-dioxanone, gamma-butyrolactone,
beta-butyrolactone, beta-me-delta-valerolactone,
1,4-dioxane-2,3-dione ethylene oxalate, 3-[benzyloxycarbonyl
methyl]-1,4-dioxane-2,5-dione, ethylene oxide, propylene oxide,
5,5'(oxepane-2-one), 2,4,7,9-tetraoxa-spiro[5,5]undecane-3,8-dione
Spiro-bid-dimethylene caronate can produce co-polymers. Copolymers
can also be produced by adding monomers such as the multifunctional
hydroxyl, carboxylic compounds or the heterofunctional compounds
that can be used as coupling agents for low molecular weight
PLA.
[0096] FIG. 5 shows a schematic view of a reaction system for
polymerizing lactic acid. The reaction system (510) includes a
stainless steel jacked reaction tank (520), a vented screw extruder
(528), a pelletizer (530), a heat exchanger (534) and a
condensation tank (540). An outlet (521) of the reaction tank is
connected to a tube (e.g., stainless steel) which is connected to
an inlet (545) to a heat exchanger. An outlet (546) to the heat
exchanger is connected to another tube (e.g., stainless steel or
other corrosive resistant material) and is connected to an inlet
(548) to the condensation tank (540). The tubes and connections
from the reaction tank and condensation tank provide a fluid
pathway (e.g., water vapor/air) between the two tanks. A vacuum can
be applied to the fluid pathway between the tanks (520) and (540)
by utilizing a vacuum pump (550) that is connected to port
(549).
[0097] The reaction tank (520) includes an outlet (524) that can be
connected to a tube (e.g., stainless steel) that is connected to an
inlet to a screw extruder (560). An outlet to the extruder (562) is
connected to a tube which is connected optionally through a valve
(560) to the reaction tank (520) through inlet (527). Optionally
the outlet to the extruder (562) is connected through valve (560)
to the pelletizer (530) through inlet (532). Tubes and connections
from the reaction tank and extruder provide a circular fluid
pathway (e.g., reactants and products) between the reaction tank
and extruder when the valve (560) is set in recirculating position.
The tubes and connections from the reaction tank to the pelletizer
provide a fluid pathway between the reaction tank and pelletizer
when the valve (560) is set in pelletizing position.
[0098] When in operation, the tank can be charged with lactic acid.
The lactic acid is heated in the tank utilizing the stainless steel
heating jacket (522). In addition, a vacuum is applied to the
condensation tank (540) and therefore to the reaction tank (520)
through the stainless steel tubing and connections using the vacuum
pump (550). The heating of the lactic acid accelerates the
condensation reactions (e.g., esterification reactions) to form
oligomers of PLA while the applied vacuum helps volatilize the
water that is produced. Water vapor travels out of the reactants
and out of the reaction tank (520) and towards the heat exchanger
(534) as indicated by the arrow. The heat exchanger cools the water
vapor and the condensed water drops into the condensation tank
(540) through the tubes and connections previously described.
Multiple heat exchangers can be utilized. Since the
hydroxy-carboxylic acids can be corrosive the reactor equipment and
other associated equipment may be clad or coated with corrosive
resistant metals such as tantalum, alloys such as HASTELLOY.TM., a
trademarked alloy from Haynes International, and the like. It can
also be coated with inert high temperature polymeric coatings such
as TEFLON.TM. from DuPont, Wilmington Del. The corrosivity of the
hydroxy-carboxylic acid system may not be surprising since the pKa
of lactic acid is more than 0.8 less than acetic acid. Also, water
undoubtedly hydrates the acid and the acid end of the polymer. When
those waters of hydration are removed the acidity can be much
higher, since it is not leveled by the waters of hydration.
[0099] In addition, during operation, extruder (528) can be engaged
and operated to draw the reactants (e.g., lactic acid, oligomers
and polymers) out of the tank. When the valve (560) is set in
recirculating position the reactants are circulated back to the
reaction tank in the direction shown by the arrows. In addition to
the extruder, the flow can be controlled by valve (525), for
example, the valve can be set to closed for no flow, open for
maximal flow or an intermediate position for lower or high flow
rates (e.g., between about 0 and 100% open, e.g., about 0%, 10%,
20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or about 100% open).
[0100] The reaction can be continued with reactants following a
circular pathway (e.g., with valve in recirculating position) until
a desired polymerization is achieved. This circulating pathway
provides mixing and shearing that can help the polymerization
(e.g., increase molecular weight, control polydispersity, improve
the kinetics of the polymerization, improve temperature
distribution and diffusion of reacting species).The products (e.g.
polymer) can then be directed to the pelletizer by setting valve
(560) to the pelletizing position. The pelletizer then can produce
pellets which can be collected. Pellets can be of various shapes
and sizes. For example, spherical or approximately spherical,
hollow tube shaped, filled tube shape with, for example,
approximate volumes, between about 1 mm.sup.3 to about 1 cm.sup.3.
The pelletizer can also be replaced with other equipment, for
example, extruders, mixers, reactors, and filament makers.
[0101] The extruder (528) can be a vented screw extruder so that
water or other volatile compounds can be removed from further
processing. The extruder can be a single screw extruder or a
multiple screw extruder. For example, the extruder can be a twin
screw extruder with co-rotating or counter rotating screws. The
screw extruder can also be a hollow flight extruder and can be
heated or cooled. The screw extruder can be fitted with ports to
its interior. The ports can be utilized, for example, for the
addition of additives, addition of co-monomers, addition of
cross-linking agents, addition of catalysts, irradiation treatments
and addition of solvents. The ports can also be utilized for
sampling (e.g., to test the progress of the reaction or
troubleshoot). In addition to sampling, the torque applied to the
extruder can be used to monitor the progress of the polymerization
(e.g., as the viscosity increases). An inline (e.g., a static
mixer) mixer can also be disposed in the pathway of the circulating
reactants, for example, before or after the screw extruder,
providing a tortuous path for the reactants which can improve the
mixing supplied to the reactants. The extruder can be sized, for
example, so that the material is recirculated, e.g., about 0.25-10
times per hour (e.g., about 1-5 or 1-4 times per hour).
[0102] The position of the return port (527) allows the reactants
to flow down the side of the tank, increasing the surface area of
the reactants facilitating the removal of water. The return port
can include multiple (e.g. a plurality of ports) disposed at
various positions in the tanks. For example, the plurality of
return ports can be placed circumferentially around the tank.
[0103] The tank can include a reciprocating scraper (529) which can
help push the formed polymer/oligomers down the reaction tank, for
example, during or after completion of the reaction. Once the
reciprocating scraper moves down, the scraper can then be moved
back up, for example, to a resting position. The scraper can be
moved up and down the tank by engaging with and axel (640) that is
attached to the hub (650). In another possible embodiment, the hub
can be tapped for mechanical coupling to a screw, for example,
wherein the axel is a screw-axel that extends to the bottom of the
tank. The screw-axel can then turn to drive the scraper down or
up.
[0104] A top view of one embodiment of a reciprocating scraper is
shown in FIG. 6A while a front cut out view is shown in FIG. 6B.
The reciprocating scraper includes pistons (620) attached to a hub
(650) and scraping ends (630). The scraping end is in the form of a
compression ring with a gap (660). The pistons apply pressure
against the inside surfaces of the tank (615) through the scraping
ends (630) while the scraper can be moved down the tank as shown by
the arrow in FIG. 6B. The gap (660) allows the expansion and
contraction of the scraper. The scraper can be made of any flexible
material, for example, steel such as stainless steel. The gap is
preferably as small as possible (e.g., less than about 1'', less
than about 0.1'', less than about 0.01'' or even less than about
0.001'').
[0105] Another embodiment of a reciprocating scraper is shown in
FIG. 6C and FIG. 6D. In this second embodiment the scraping ends
include a lip-seal. The lip seal can be made of a flexible
material, for example, rubber. The movement of the lip-seal as the
scraper moves up and down acts as a squeegee against the inside of
the reaction tank.
[0106] The tank (520) can be 100 gal in size, although larger and
smaller sizes can be utilized (e.g., between about 20 to 10, 000
gal, e.g., at least 50 gal, at least 200 gal, at least 500 gal, at
least 1000 gal). The tank, for example, can be shaped with a
conical bottom or rounded bottom.
[0107] In addition to the inlets and outlets discussed, the tank
can also include other openings, for example, to allow the addition
of reagents or for access to the interior of the tank for
repairs.
[0108] During the reaction the temperature in the tank can be
controlled from between about 100 and 180.degree. C. The
polymerization can preferably started at about 100.degree. C. and
the temperature increased to about 160.degree. C. over several
hours (e.g., between 1 and 48 hours, 1 and 24 hours, 1 and 16
hours, 1 and 8 hours). A vacuum can be applied between about 0.1
and 2 mmHg). For example, at the beginning of the reaction about
0.1 mmHg and at the end of the reaction about 2 mmHg.
[0109] Water from the condenser tank (540) can be drained trough an
opening (542) utilizing control valve (544).
[0110] The heat exchanger can be a fluid cooled heat exchanger. For
example, cooled with water, air or oil. Several heat exchangers can
be used, for example, as needed to condense as much of the water as
possible. For example, a second heat exchanger can be located
between the vacuum pump and the condensation tank (540).
[0111] The equipment and reactions described herein (e.g., FIG. 5)
can also be used for polymerization of other monomers. In addition,
the equipment can be utilized after or during the polymerizations
for blending of polymers. For example, any of the hydroxyl acids
described herein can be polymerized by the methods, equipment and
system described herein.
[0112] In addition to chemical method, lactic acid can be
polymerized by LA-polymerizing enzymes and organisms. For example,
ROP can be catalyzed by Candida antarctica lipase B, and
hydrolases.
PLA Sterochemistry
[0113] Mechanical and thermal properties of pure PLA are largely
determined by the molecular weight and stereochemical composition
of the backbone. The stereochemical composition of the backbone can
be controlled by the choice and ratios of monomers; D-Lactic acid,
L-Lactic acid or alternatively D-Lactide, L-Lactide or
meso-Lactide. This stereochemical control allows the formation of
random or block stereo copolymers. The molecular weight of the
polymers can be controlled, for example, as discussed above. The
ability to control the stereochemical architecture allows, for
example, precise control over the speed and degree of
crystallinity, the mechanical properties, and the melting point and
glass transition temperatures of the material.
[0114] The degree of crystallinity of PLA influences the hydrolytic
stability of the polymer, and therefore, the biodegradability of
the polymer. For example, highly crystalline PLA can take from
months to years to degrade, while amorphous samples can be degraded
in a few weeks to a few months. This behavior is due in part to the
impermeability of the crystalline regions of PLA. Table 1 shows
some of the thermal properties of some PLA of similarly treated
samples. The percent crystallinity can be calculated by using data
form the table and applying the equation.
% .chi. c = ( .DELTA. H m - .DELTA. H c ) 93 100 ##EQU00001##
[0115] Where .DELTA.H.sub.m is the melting enthalpy in J/g,
.DELTA.H.sub.c is the crystallization enthalpy in J/g and 93 is the
crystallization enthalpy of a totally crystalline PLA sample in
J/g.
[0116] As can be calculated from the data in the table, the
crystallinity is directly proportional to the molecular weight of
the pure L or pure D stereo polymer. The DL stereoisomer (e.g.,
atactic polymer) is amorphous.
TABLE-US-00001 TABLE 1 Thermal properties of PLA Isomer M.sub.n x
M.sub.w/ Tg T.sub.m .DELTA.H T.sub.c .DELTA.H type 10.sup.3 M.sub.n
(.degree. C.) (.degree. C.) (J/g) (.degree. C.) (J/g) L 4.7 1.09
45.6 157.8 55.5 98.3 47.8 DL 4.3 1.90 44.7 -- -- -- -- L 7.0 1.09
67.9 159.9 58.8 108.3 48.3 DL 7.3 1.16 44.1 -- -- -- -- D 13.8 1.19
65.7 170.3 67.0 107.6 52.4 L 14.0 1.12 66.8 173.3 61.0 110.3 48.1 D
16.5 1.20 69.1 173.5 64.6 109.0 51.6 L 16.8 1.32 58.6 173.4 61.4
105.0 38.1
[0117] Calculated crystallinities are in order top to bottom: 8.2%,
0%, 11.3%, 0%, 15.7%, 13.8%, 14.0% and 25%.
[0118] The thermal treatment of samples, for example, rates of
melting, recrystallization, and annealing history, can in part
determine the amount of crystallization. Therefore, comparisons of
the thermal, chemical and mechanical properties of PLS polymers
should generally be most meaningful for polymers with a similar
thermal history.
[0119] The pure L-PLA or D-PLA has a higher tensile strength and
low elongation and consequently has a higher modulus than DL-PLA.
Values for L-PLA vary greatly depending on how the material is made
e.g., tensile strengths of 30 to almost 400 MPa, and tensile
modulus between 1.7 to about 4.5 GPa.
PLA Copolymers, Crosslinking and Grafting
[0120] Variation of PLA by the formation of copolymers as discussed
above also has a very large influence on the properties, for
example, by disrupting and decreasing the crystallinity and
modulating the glass transition temperatures. For example, polymers
with increased flexibility, improved hydrophilicity, better
degradability, better biocompatibility, better tensile strengths,
improved elongations properties can be produced.
[0121] In many cases, the improvements are correlated with a
decrease in the glass transition temperature. A few monomers can
increase the glass transition temperature of PLA. For example,
lactones of salicylic acids can have homopolymer glass transition
temperatures between about 70 and 110.degree. C. and polymerize
with lactide.
[0122] Morpholinediones, which are half alpha-hydroxy carboxylic
acids and half alpha-amino acids co-polymerize with lactide to give
high molecular weight random co-polymers with lower glass
transition temperatures (e.g., following the Flory-Fox equation).
morpholinediones made up of glycine and lactic acid
(6-methyl-2,5-morpholinedione) when copolymerized with lactide can
give a polymer with glass transition temperatures of 109 and
71.degree. C. for a 50 and 75 mol % lactic acid respectively in the
polymer. Morpholinediones have been synthesized using glycolic acid
or lactic acid and most of the alpha amino acids (e.g., glycine,
alanine, aspartic acid, lysine, cysteine, valine and leucine). In
addition to lowering the glass transition temperature and improving
mechanical properties, the use of functional amino acids in the
synthesis of morpholinediones is an effective way of incorporating
functional pendant groups into the polymer.
[0123] As an example, copolymers of glycolide and lactide can be
useful as biocompatible surgical sutures due to increased
flexibility and hydrophilicity. The higher melting point of
228.degree. C. and Tg of 37.degree. C. for polyglycolic acid can
produce a range of amorphous co-polymers with lower glass
transition temperatures than PLA. Another copolymerization example
is copolymerization with e-caprolactone which can yield tough
polymers with properties ranging from ridged plastics to
elastomeric rubbers and with tensile strengths ranging from 80 to
7000 psi, and elongations over 400%. Co-polymers of
beta-methyl-gamma-valerolactone have been reported to produce
rubber-like properties. Co-polymers with polyethers such as
poly(ethylene oxide), poly(propylene oxide) and poly(tetramethylene
oxide) are biodegradable, biocompatible and flexible polymers.
[0124] Some additional useful monomers that can be copolymerized
with lactide include 1,4-benzodioxepin-2,3(H)-dione
glycosalicylide; 1.3-benzodioxepin-2,5-(3H, 3-methyl)-dione
Lactosalicylide; dibenzo-1,5-dioxacin-6,12-dione disalicylide;
morpholine-2,5-dione, 1,4-dioxane-2,5-dione, glycolide;
oxepane-2-one trimethylene carbonate; 2,2-dimethyltrimethylene
carbonate; 1,5-dioxepane-2-one; 1,4-dioxane-2-one p-dioxanone;
gamma-butyrolactone; beta-butyrolactone;
beta-methyl-delta-valerolactone; beta-methyl-gamma-valerolactone;
1,4-dioxane-2,3-dione ethylene oxalate;
3[(benzyloxycarbonyl)methyl]-1,4-dioxane-2,5-dione; ethylene oxide;
propylene oxide, 5,5'-(oxepane-2-one) and
2,4,7,9-tetraoxa-spiro[5,5] undecane-3,8-dione
Spiro-bis-dimethylene caronate.
[0125] PLA polymers and co-polymers can be modified by cross
linking Cross linking can affect the thermal and rheological
properties without necessarily deteriorating the mechanical
properties. For example, 0.2 mol %
5,5'-bis(oxepane-2-one)(bis-.epsilon.-caprolactone)) and 0.1-0.2
mol % spiro-bis-dimethylene carbonate cross linking Free radical
hydrogen abstraction reactions and subsequent polymer radical
recombination is an effective way of inducing crosslinks into a
polymer. Radicals can be generated, for example, by high energy
electron beam and other irradiation (e.g., between about 0.01 Mrad
and 15 Mrad, e.g. between about 0.01-5 Mrad, between about 0.1-5
Mrad, between about 1-5 Mrad). For example, irradiation methods and
equipment are described in detail below.
[0126] Alternatively or in addition, peroxides, such as organic
peroxides are effective radical producing and cross linking agents.
For example, peroxides that can be used include hydrogen peroxide,
dicumyl peroxide; benzoyl peroxide;
2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane; tert-butylperoxy
2-ethylhexyl carbonate; tert-amyl peroxy-2-ethylhexanoate;
1,1-di(tert-amylperoxy)cyclohexane; tert-amyl peroxyneodecanoate;
tert-amyl peroxybenzoate; tert-amylperoxy 2-ethylhexyl carbonate;
tert-amyl peroxyacetate;
2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; tert-butyl
peroxy-2-ethylhexanoate; 1,1-di(tert-butylperoxy)cyclohexane;
tert-butyl peroxyneodecanoate; tert-butyl peroxyneoheptanoate;
tert-butyl peroxydiethylacetate;
1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane;
3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane;
di(3,5,5-trimethylhexanoyl) peroxide; tert-butyl peroxyisobutyrate;
tert-butyl peroxy-3,5,5-trimethylhexanoate; di-tert-butyl peroxide;
tert-butylperoxy isopropyl carbonate; tert-butyl peroxybenzoate;
2,2-di(tert-butylperoxy)butane; di(2-ethylhexyl) peroxydicarbonate;
di(2-ethylhexyl) peroxydicarbonate; tert-butyl peroxyacetate;
tert-butyl cumyl peroxide; tert-amylhydroperoxide;
1,1,3,3-tetramethylbutyl hydroperoxide, and mixtures of these. The
effective amounts can vary, for example, depending on the peroxide,
cross-linking reaction conditions and the desired properties (e.g.,
amount of cross linking). For example, cross-linking agents can be
added from between about 0.01-10 wt. % (e.g., about 0.1-10 wt. %,
about 0.01-5wt. %, about 0.1-1 wt. %, about 1-8 wt. %, about 4-6
wt. %). For example, peroxides such as 5.25 wt. % dicumyl peroxide
and 0.1% benzoyl peroxide are effective radical producing and cross
linking agents for PLA and PLA derivatives. The peroxide
cross-lining agents can be added to polymers as solids, liquids or
solutions, for example, in water or organic solvents such as
mineral spirits. In addition radical stabilizers can be
utilized.
[0127] Cross linking can also be effectively accomplished by the
incorporation of unsaturation in the polymer chain either by:
initiation with unsaturated alcohols such as hydroxyethyl
methacrylate or 2-butene-1,4-diol; the post reaction with
unsaturated anhydrides such as maleic anhydride to transform the
hydroxyl chain end; or copolymerization with unsaturated epoxides
such as glycidyl methacrylate.
[0128] In addition to cross linking, grafting of functional groups
and polymers to a PLA polymer or co-polymer is an effective method
of modifying the polymer properties. For example, radicals can be
formed as described above and a monomer, functionalizing polymer or
small molecule. For example, irradiation or treatment with a
peroxide and then quenching with a functional group containing an
unsaturated bond can effectively functionalize the PLA
backbone.
PLA Blending
[0129] PLA can be blended with other polymers as miscible or
immiscible compositions. For immiscible blends, the composition can
be one with the minor component (e.g., bellow about 30 wt. %) as
small (e.g., micron or sub-micron) domains in the major component.
When one component is about 30 to 70 wt. % the blend forms a
co-continuous morphology (e.g., lamellar, hexagon phases or
amorphous continuous phases).
[0130] Blending can be accomplished by melt mixing above the glass
transition temperature of the amorphous polymer components. Screw
extruders (e.g., single screw extruders, co-rotating twin screw
extruders, counter rotating twin screw extruders) can be useful for
this. For PLA polymers and co-polymers temperatures below about
200.degree. C. can be used to avoid thermal degradation (e.g. below
about 180.degree. C.). Therefore, polymers that require higher
processing temperatures are not generally good candidates for
blending with PLA.
[0131] Polyethylene oxide (PEO) and polypropylene oxide (PPO) can
be blended with PLA. Lower molecular weight glycols (300-1000 Mw)
are miscible with PLA while PPO becomes immiscible at higher
molecular weight. These polymers, especially PEO, can be used to
increase the water transmission and bio-degradation rate of PLA.
They can also be used as polymeric plasticizers to lower the
modulus and increase flexibility of PLA. High molecular weight PEG
(20,000) is miscible in PLA up to about 50%, but above that level
the PEG crystallizes, reducing the ductility of the blend.
[0132] Polyvinyl acetate (PVA) is miscible with PLA in all
concentrations, where the blends show only one Tg is observed at
all blend ratios, with a constant decrease to about 37.degree. C.
at 100% PVA. Low levels of PVA (5-10%) increase the tensile
strength and % elongation of PLA while significantly reducing the
rate of weight loss during bio-degradation.
[0133] Blends of PLA and polyolefins (polypropylene and
polyethylene) result in incompatible systems with poor physical
properties due to the poor interfacial compatibility and high
interfacial energy. However, the interfacial energy can be lowered,
for example, by the addition of third component compatibilizers,
such as glycidyl methacrylate grafted polyethylene. (irradiation
would probably work) Polystyrene and high impact polystyrene resins
are also non-polar and blends with PLA are generally not very
compatible
[0134] PLA and acetals can be blended making compositions with
useful properties. For example, good, high transparency.
[0135] PLA is miscible with polymethyl methacrylate and many other
acrylates and copolymers of (meth)acrylates. Drawn films of
PMMA/PLA blends are transparent and have high elongation.
[0136] Polycarbonate can be combined with PLA up to about a 50 wt.
% composition of Polycarbonate. The compositions have high heat
resistance, flame resistance and toughness and have applications,
for example, in consumer electronics such as laptops. About 50 wt.
% polycarbonate, the processing temperatures approach the
degradation temperature of PLA.
[0137] Acrylonitrile butadiene styrene (ABS) can be blended with
PLA although the polymers are not miscible. This combination is a
less brittle material than PLA and provides a way to toughen
PLA.
[0138] Poly(propylene carbonate) can be blended with PLA providing
a biodegradable composite since both polymers are
biodegradable.
[0139] PLA can also be blended with Poly(butylene succinate).
Blends can impart thermal stability and impact strength to the
PLA.
[0140] PEG, poly propylene glycol, poly(vinyl acetate), anhydrides
(e.g., maleic anhydride) and fatty acid esters have been added as
plasticizers and/or compatibilizers.
[0141] Blending can also be accomplished with the application of
irradiation, including irradiation and quenching. For example,
irradiation or irradiation and quenching, as described herein
applied to biomass can be applied to the irradiation of PLA and PLA
copolymers for any purpose, for example, before, after and/or
during blending. This treatment can aid in the processing, for
example, making the polymers more compatible and/or making/breaking
bonds within the polymer and/or blended additive (e.g., polymer,
plasticizer). For example, between about 0.1 Mrad and 150 Mrad
followed by quenching of the radicals by the addition of fluids or
gases (e.g., oxygen, nitrous oxide, ammonia, liquids), using
pressure, heat, and/or the addition of radical scavengers.
Quenching of biomass that has been irradiated is described in U.S.
Pat. No. 8,083,906 to Medoff, the entire disclosure of which is
incorporated herein by reference, and the equipment and processes
describe therein can be applied to PLA and PLA derivatives.
Irradiation and extruding or conveying of the PLA or PLA copolymers
can also be utilized, for example, as described for the treatment
of biomass in U.S. application Ser. No. 13/009,151 filed on May 2,
2011 the entire disclosure of which is incorporated herein by
reference.
PLA Composites
[0142] PLA polymers, co-polymers and blends can be combined with
synthetic and/or natural materials. For example, PLA and any PLA
derivative (e.g., PLA copolymers, PLA blends, grated PLA,
cross-linked PLA) can be combined with synthetic and natural
fibers. For example, protein, starch, cellulose, plant fibers
(e.g., abaca, leaf, skin, bark, kenaf fibers), inorganic fillers,
flax, talc, glass, mica, saponite and carbon fibers. This can
provide a material with, for example, improved mechanical
properties (e.g., toughness, harness, strength) and improved
barrier properties (e.g., lower permeability to water and/or
gasses).
[0143] Nano composites can also be made by dispersing inorganic or
organic nanoparticles into either a thermoplastic or thermoset
polymer. Nanoparticles can be spherical, polyhedral, two
dimensional nanofibers or disc-like nanoparticles. For example,
colloidal or microcrystalline silica, alumina or metal oxides
(e.g., TiO.sub.2); carbon nanotubes; clay platelets.
[0144] Composites can be prepared similarly to polymer blends, for
example, utilizing screw extrusion and/or injection molding.
Irradiation as described herein can also be applied to the
composites, during, after or before their formation. For example,
irradiation of the polymer and combination with the synthetic
and/or natural materials, or irradiation of the synthetic and/or
natural materials and combination with the polymer, or irradiation
of both the polymer and synthetic and/or natural material and then
combining, or irradiating the composite after it has been combined,
with or without further processing.
PLA with Plasticizers and Elastomers
[0145] In addition to the blends previously discussed, PLA and PLA
derivatives can be combined with plasticizers.
[0146] For example, as described in J. Appl. Polym. Sci. 66:
1507-1513, 1997, PLA can be blended with monomeric and oligomeric
plasticizers in order to enhance its flexibility and thereby
overcome its inherent brittleness. Monomeric plasticizers, such as
tributyl citrate, TbC, and diethyl bishydroxymethyl malonate, DBM,
can drastically decreased the T.sub.g of PLA. Increasing the
molecular weight of the plasticizers by synthesizing oligoesters
and oligoesteramides can result in blends with T.sub.g depressions
slightly smaller than with the monomeric plasticizers. The
compatibility with PLA can be dependent on the molecular weight of
the oligomers and on the presence of polar groups (e.g., amide
groups, hydroxyl groups, ketones, esters) that can interact with
the PLA chains. The materials can retain a high flexibility and
morphological stability over long periods of time, for example,
when formed into films.
[0147] Citrate esters can also be used as plasticizers with
poly(lactic acid) (PLA). Films can be extruded, for example, using
a single or twin-screw extruder with plasticizer contents (citrate
esters or others described herein) of between about 1 and 40 wt. %
(e.g., about 5-30 wt. %, about 5-25 wt. %, about 5-15 wt. %).
Plasticizers such as citrate esters can be effective in reducing
the glass transition temperature and improving the elongation at
break. The plasticizing efficiency can be higher for the
intermediate-molecular-weight plasticizers. The addition of
plasticizers can modulate the enzymatic degradation of PLA. For
example, lower-molecular-weight citrates can increase the enzymatic
degradation rate of PLA and the higher-molecular-weight citrates
can decreased the degradation rate as compared with that of
unplasticized PLA.
[0148] Preparation of poly(lactic acid)/elastomer blends can also
be prepared by melt blending technique, for example, as described
in the Journal of Elastomers and Plastics, Jan. 3, 2013. PLA and
biodegradable elastomer can be melt blended and molded in an
injection molding machine. The melting temperature can decrease as
the amount of elastomer increases. Additionally, the presence of
elastomer can modulate the crystallinity of PLA, for example,
increasing the crystallinity by between about 1 and 30% (e.g.,
between about 1 to 20%, between about 5 and 15%). The complex
viscosity and storage modulus of PLA melt can decrease upon
addition of elastomer. The elongation at break can increase as the
content of elastomer increased while Young's modulus and tensile
strength often decrease due to the addition of elastomer.
[0149] It has been observed that the cold crystallization
temperature of the blends decreased as the weight fraction of
elastomer increased as well as the onset temperature of cold
crystallization also shifted to lower temperature. For example, as
reported in the Journal of Polymer Research, February 2012,
19:9818. In non-isothermal crystallization experiments, the
crystallinity of PLA increased with a decrease in the heating and
cooling rate. The melt crystallization of poly(lactic acid)
appeared in the low cooling rate (1, 5 and 7.5.degree. C./min). The
presence of small amounts of elastomer can also increase the
crystallinity of poly (lactic acid). The DSC thermogram at ramp of
10.degree. C./min showed the maximum crystallinity of poly(lactic
acid) is 36.95% with 20 wt. % elastomer contents in blends. In
isothermal crystallization, the cold crystallization rate increased
with increasing crystallization temperature in the blends. The
Avrami analysis showed that the cold crystallization was in two
stages process and it was clearly seen at low temperature. The
Avrami exponent (n) at first stage was varying from 1.59 to 2 which
described a one-dimensional crystallization growth with homogeneous
nucleation, whereas at second stage was varying from 2.09 to 2.71
which described the transitional mechanism to three dimensional
crystallization growth with heterogeneous nucleation mechanism. The
equilibrium melting point of poly(lactic acid) was also evaluated
at 176.degree. C.
[0150] Some examples of elastomers that can be combined with PLA
include: Elastomer NPEL001, Polyurethane elastomers (5-10%),
Functionalized polyolefin elastomers, Blendex.RTM. (e.g., 415, 360,
338), PARALOID.TM. KM 334, BTA 753, EXL 3691A, 2314, Ecoflex.RTM.
Supersoft Silicone Bionolle.RTM. 3001, Pelleethane.RTM. 2102-75A,
Kraton.RTM. FG 1901X, Hytrel.RTM. 3078, and mixtures of these.
Mixtures with any other elastomer, for example, as described herein
can also be used.
[0151] Some examples of plasticizers that can be combined with PLA
include: Triacetin, glycerol triacetate, tributyl citrate,
polyethylene glycol, GRINDSTED.RTM. SOFT-N-SAFE (acetic acid ester
of monoglycerides) made from fully hydrogenated castor oil and
combinations of these. Mixtures with any other plasticizers, for
example, as described herein can also be used.
[0152] The main characteristic of elastomer materials is the high
elongation and flexibility or elasticity of these materials,
against its breaking or cracking.
[0153] Depending on the distribution and degree of the chemical
bonds of the polymers, elastomeric materials can have properties or
characteristics similar to thermosets or thermoplastics, so
elastomeric materials can be classified into: Thermoset Elastomers
(e.g., do not melt when heated) and Thermoplastic Elastomers (e.g.,
melt when heated). Some properties of elastomer materials: Cannot
melt, before melting they pass into a gaseous state; swell in the
presence of certain solvents; are generally insoluble; are flexible
and elastic; lower creep resistance than the thermoplastic
materials.
[0154] Examples of applications of elastomer materials described
herein are: possible substitutes or replacements for natural rubber
(e.g., material used in the manufacture of gaskets, shoe heels);
possible substitutes or replacements for polyurethanes (e.g., for
use in the textile industry for the manufacture of elastic
clothing, for use as foam, and for use in making wheels); possible
substitutes or replacements for polybutadiene (e.g., elastomer
material used on the wheels or tires of vehicles); possible
substitutes or replacements for neoprene (e.g., used for the
manufacture of wetsuits, wire insulation, industrial belts);
possible substitutes or replacements for silicone (e.g., pacifiers,
medical prostheses, lubricants). In addition, the materials
described herein can be used as substitutes for polyurethane and
silicon adhesives.
Flavors, Fragrances and Colors
[0155] Any of the products and/or intermediates described herein,
for example, hydroxyl acids, lactic acid, PLA, PLA derivatives
(e.g., PLA copolymers, PLA composites, cross-linked PLA, grafted
PLA, PLA blends or any other PLA containing material prepared as
described herein) can also be combined with flavors, fragrances
colors and/or mixtures of these. For example, any one or more of
(optionally along with flavors, fragrances and/or colors) sugars,
organic acids, fuels, polyols, such as sugar alcohols, biomass,
fibers and composites, hydroxy-carboxylic acids, lactic acid, PLA,
PLA derivatives can be combined with (e.g., formulated, mixed or
reacted) or used to make other products. For example, one or more
such product can be used to make soaps, detergents, candies, drinks
(e.g., cola, wine, beer, liquors such as gin or vodka, sports
drinks, coffees, teas), pharmaceuticals, adhesives, sheets (e.g.,
woven, none woven, filters, tissues) and/or composites (e.g.,
boards). For example, one or more such product can be combined with
herbs, flowers, petals, spices, vitamins, potpourri, or candles.
For example, the formulated, mixed or reacted combinations can have
flavors/fragrances of grapefruit, orange, apple, raspberry, banana,
lettuce, celery, cinnamon, vanilla, peppermint, mint, onion,
garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean beef,
fish, clams, olive oil, coconut fat, pork fat, butter fat, beef
bouillon, legume, potatoes, marmalade, ham, coffee and cheeses.
[0156] Flavors, fragrances and colors can be added in any amount,
such as between about 0.01 wt. % to about 30 wt. %, e.g., between
about 0.05 to about 10, between about 0.1 to about 5, or between
about 0.25 wt. % to about 2.5 wt. %. These can be formulated, mixed
and/or reacted (e.g., with any one of more product or intermediate
described herein) by any means and in any order or sequence (e.g.,
agitated, mixed, emulsified, gelled, infused, heated, sonicated,
and/or suspended). Fillers, binders, emulsifier, antioxidants can
also be utilized, for example, protein gels, starches and
silica.
[0157] The flavors, fragrances and colors can be natural and/or
synthetic materials. These materials can be one or more of a
compound, a composition or mixtures of these (e.g., a formulated or
natural composition of several compounds). Optionally, the flavors,
fragrances, antioxidants and colors can be derived biologically,
for example, from a fermentation process (e.g., fermentation of
saccharified materials as described herein). Alternatively, or
additionally these flavors, fragrances and colors can be harvested
from a whole organism (e.g., plant, fungus, animal, bacteria or
yeast) or a part of an organism. The organism can be collected and
or extracted to provide color, flavors, fragrances and/or
antioxidant by any means including utilizing the methods, systems
and equipment described herein, hot water extraction, chemical
extraction (e.g., solvent or reactive extraction including acids
and bases), mechanical extraction (e.g., pressing, comminuting,
filtering), utilizing an enzyme, utilizing a bacteria such as to
break down a starting material, and combinations of these methods.
The compounds can be derived by a chemical reaction, for example,
the combination of a sugar (e.g., as produced as described herein)
with an amino acid (Maillard reaction). The flavor, fragrance,
antioxidant and/or color can be an intermediate and or product
produced by the methods, equipment or systems described herein, for
example, and ester and a lignin derived product.
[0158] Some examples of flavor, fragrances or colors are
polyphenols. Polyphenols are pigments responsible for the red,
purple and blue colors of many fruits, vegetables, cereal grains,
and flowers. Polyphenols also can have antioxidant properties and
often have a bitter taste. The antioxidant properties make these
important preservatives. On class of polyphenols are the
flavonoids, such as Anthrocyanins, flavonols, flavan-3-ols,
flavones, flavanones and flavanonols. Other phenolic compounds that
can be used include phenolic acids and their esters, such as
chlorogenic acid and polymeric tannins.
[0159] Inorganic compounds, minerals or organic compounds can be
used, for example, titanium dioxide, cadmium yellow (e.g., CdS),
cadmium orange (e.g., CdS with some Se), alizarin crimson (e.g.,
synthetic or non-synthetic rose madder), ultramarine (e.g.,
synthetic ultramarine, natural ultramarine, synthetic ultramarine
violet), cobalt blue, cobalt yellow, cobalt green, viridian (e.g.,
hydrated chromium(III)oxide), chalcophyllite, conichalcite,
cornubite, cornwallite and liroconite.
[0160] Some flavors and fragrances that can be utilized include
ACALEA TBHQ, ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL,
AMBRETTOLIDE, AMBRINOL 95, ANDRANE, APHERMATE, APPLELIDE,
BACDANOL.RTM., BERGAMAL, BETA IONONE EPOXIDE, BETA NAPHTHYL
ISO-BUTYL ETHER, BICYCLONONALACTONE, BORNAFIX.RTM., CANTHOXAL,
CASHMERAN.RTM., CASHMERAN.RTM. VELVET, CASSIFFIX.RTM., CEDRAFIX,
CEDRAMBER.RTM., CEDRYL ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL
DIMETHYL ACETATE, CITROLATE.TM., CITRONELLOL 700, CITRONELLOL 950,
CITRONELLOL COEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE,
CITRONELLYL FORMATE, CLARYCET, CLONAL, CONIFERAN, CONIFERAN PURE,
CORTEX ALDEHYDE 50% PEOMOSA, CYCLABUTE, CYCLACET.RTM.,
CYCLAPROP.RTM., CYCLEMAX.TM., CYCLOHEXYL ETHYL ACETATE, DAMASCOL,
DELTA DAMASCONE, DIHYDRO CYCLACET, DIHYDRO MYRCENOL, DIHYDRO
TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYL CYCLORMOL, DIMETHYL
OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE, DULCINYL.RTM.
RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE, FLEURAMONE, FLEURANIL,
FLORAL SUPER, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONE,
GALAXOLIDE.RTM. 50, GALAXOLIDE.RTM. 50 BB, GALAXOLIDE.RTM. 50 IPM,
GALAXOLIDE.RTM. UNDILUTED, GALBASCONE, GERALDEHYDE, GERANIOL 5020,
GERANIOL 600 TYPE, GERANIOL 950, GERANIOL 980 (PURE), GERANIOL CFT
COEUR, GERANIOL COEUR, GERANYL ACETATE COEUR, GERANYL ACETATE,
PURE, GERANYL FORMATE, GRISALVA, GUAIYL ACETATE, HELIONAL.TM.,
HERBAC, HERBALIME.TM., HEXADECANOLIDE, HEXALON, HEXENYL SALICYLATE
CIS 3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPIC
ALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE,
INTRELEVEN ALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO
CITRAL, ISO CYCLO GERANIOL, ISO E SUPER.RTM., ISOBUTYL QUINOLINE,
JASMAL, JESSEMAL.RTM., KHARISMAL.RTM., KHARISMAL.RTM. SUPER,
KHUSINIL, KOAVONE.RTM., KOHINOOL.RTM., LIFFAROME.TM., LIMOXAL,
LINDENOL.TM., LYRAL.RTM., LYRAME SUPER, MANDARIN ALD 10% TRI ETH,
CITR, MARITIMA, MCK CHINESE, MEIJIFF.TM., MELAFLEUR, MELOZONE,
METHYL ANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL IONONE GAMMA
A, METHYL IONONE GAMMA COEUR, METHYL IONONE GAMMA PURE, METHYL
LAVENDER KETONE, MONTAVERDI.RTM., MUGUESIA, MUGUET ALDEHYDE 50,
MUSK Z4, MYRAC ALDEHYDE, MYRCENYL ACETATE, NECTARATE.TM., NEROL
900, NERYL ACETATE, OCIMENE, OCTACETAL, ORANGE FLOWER ETHER,
ORIVONE, ORRINIFF 25%, OXASPIRANE, OZOFLEUR, PAMPLEFLEUR.RTM.,
PEOMOSA, PHENOXANOL.RTM., PICONIA, PRECYCLEMONE B, PRENYL ACETATE,
PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL,
SANTALIFF.TM., SYVERTAL, TERPINEOL, TERPINOLENE 20, TERPINOLENE 90
PQ, TERPINOLENE RECT., TERPINYL ACETATE, TERPINYL ACETATE JAX,
TETRAHYDRO, MUGUOL.RTM., TETRAHYDRO MYRCENOL, TETRAMERAN,
TIMBERSILK.TM., TOBACAROL, TRIMOFIX.RTM. O TT, TRIPLAL.RTM.,
TRISAMBER.RTM., VANORIS, VERDOX.TM., VERDOX.TM. HC, VERTENEX.RTM.,
VERTENEX.RTM. HC, VERTOFIX.RTM. COEUR, VERTOLIFF, VERTOLIFF ISO,
VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO
50 PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE
INDIA, ABSOLUTE MD 50 PCT BB, ABSOLUTE MOROCCO, CONCENTRATE PG,
TINCTURE 20 PCT, AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL,
ARMOISE OIL 70 PCT THUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND
VERT ABS MD, BASIL OIL GRAND VERT, BASIL OIL VERVEINA, BASIL OIL
VIETNAM, BAY OIL TERPENELESS, BEESWAX ABS N G, BEESWAX ABSOLUTE,
BENZOIN RESINOID SIAM, BENZOIN RESINOID SIAM 50 PCT DPG, BENZOIN
RESINOID SIAM 50 PCT PG, BENZOIN RESINOID SIAM 70.5 PCT TEC,
BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANT BUD ABS MD 37 PCT TEC,
BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUD ABSOLUTE BURGUNDY,
BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID, BROOM ABSOLUTE
ITALY, CARDAMOM GUATEMALA CO2 EXTRACT, CARDAMOM OIL GUATEMALA,
CARDAMOM OIL INDIA, CARROT HEART, CASSIE ABSOLUTE EGYPT, CASSIE
ABSOLUTE MD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C
50 PCT MIGLYOL, CASTOREUM ABSOLUTE, CASTOREUM RESINOID, CASTOREUM
RESINOID 50 PCT DPG, CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST,
CHAMOMILE OIL ROMAN, CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW
LIMONENE, CINNAMON BARK OIL CEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE
COLORLESS, CITRONELLA OIL ASIA IRON FREE, CIVET ABS 75 PCT PG,
CIVET ABSOLUTE, CIVET TINCTURE 10 PCT, CLARY SAGE ABS FRENCH DECOL,
CLARY SAGE ABSOLUTE FRENCH, CLARY SAGE C'LESS 50 PCT PG, CLARY SAGE
OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAM OIL, CORIANDER SEED OIL,
CYPRESS OIL, CYPRESS OIL ORGANIC, DAVANA OIL, GALBANOL, GALBANUM
ABSOLUTE COLORLESS, GALBANUM OIL, GALBANUM RESINOID, GALBANUM
RESINOID 50 PCT DPG, GALBANUM RESINOID HERCOLYN BHT, GALBANUM
RESINOID TEC BHT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE
CONCRETE, GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE EGYPT, GERANIUM
OIL CHINA, GERANIUM OIL EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED
SOLUBLE, GUAIACWOOD HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY
ABSOLUTE MD 50 PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE
ABS YUGO MD 50 PCT TEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE
ABSOLUTE YUGO, JASMIN ABS INDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN
ABSOLUTE INDIA, ASMIN ABSOLUTE MOROCCO, JASMIN ABSOLUTE SAMBAC,
JONQUILLE ABS MD 20 PCT BB, JONQUILLE ABSOLUTE France, JUNIPER
BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIED SOLUBLE, LABDANUM
RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUM RESINOID MD,
LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE H, LAVANDIN
ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC, LAVANDIN OIL GROSSO
ORGANIC, LAVANDIN OIL SUPER, LAVENDER ABSOLUTE H, LAVENDER ABSOLUTE
MD, LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC,
LAVENDER OIL MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB,
MAGNOLIA FLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL,
MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF OIL, MANDARIN OIL MD,
MANDARIN OIL MD BHT, MATE ABSOLUTE BB, MOSS TREE ABSOLUTE MD TEX
IFRA 43, MOSS-OAK ABS MD TEC IFRA 43, MOSS-OAK ABSOLUTE IFRA 43,
MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRH RESINOID BB, MYRRH
RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRON FREE, MYRTLE OIL
TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSE ABSOLUTE
FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLET
ABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM
RESINOID DPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM RESINOID
MD, OLIBANUM RESINOID MD 50 PCT DPG, OLIBANUM RESINOID TEC,
OPOPONAX RESINOID TEC, ORANGE BIGARADE OIL MD BHT, ORANGE BIGARADE
OIL MD SCFC, ORANGE FLOWER ABSOLUTE TUNISIA, ORANGE FLOWER WATER
ABSOLUTE TUNISIA, ORANGE LEAF ABSOLUTE, ORANGE LEAF WATER ABSOLUTE
TUNISIA, ORRIS ABSOLUTE ITALY, ORRIS CONCRETE 15 PCT IRONE, ORRIS
CONCRETE 8 PCT IRONE, ORRIS NATURAL 15 PCT IRONE 4095C, ORRIS
NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID, OSMANTHUS ABSOLUTE,
OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEART N.degree. 3,
PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE,
PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL HEART,
PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA, PETITGRAIN
CITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OIL
TERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EX
GERANIUM CHINA, ROSE ABS BULGARIAN LOW METHYL EUGENOL, ROSE ABS
MOROCCO LOW METHYL EUGENOL, ROSE ABS TURKISH LOW METHYL EUGENOL,
ROSE ABSOLUTE, ROSE ABSOLUTE BULGARIAN, ROSE ABSOLUTE DAMASCENA,
ROSE ABSOLUTE MD, ROSE ABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH,
ROSE OIL BULGARIAN, ROSE OIL DAMASCENA LOW METHYL EUGENOL, ROSE OIL
TURKISH, ROSEMARY OIL CAMPHOR ORGANIC, ROSEMARY OIL TUNISIA,
SANDALWOOD OIL INDIA, SANDALWOOD OIL INDIA RECTIFIED, SANTALOL,
SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10 PCT, STYRAX RESINOID,
STYRAX RESINOID, TAGETE OIL, TEA TREE HEART, TONKA BEAN ABS 50 PCT
SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE ABSOLUTE INDIA, VETIVER
HEART EXTRA, VETIVER OIL HAITI, VETIVER OIL HAITI MD, VETIVER OIL
JAVA, VETIVER OIL JAVA MD, VIOLET LEAF ABSOLUTE EGYPT, VIOLET LEAF
ABSOLUTE EGYPT DECOL, VIOLET LEAF ABSOLUTE FRENCH, VIOLET LEAF
ABSOLUTE MD 50 PCT BB, WORMWOOD OIL TERPENELESS, YLANG EXTRA OIL,
YLANG III OIL and combinations of these.
[0161] The colorants can be among those listed in the Color Index
International by the Society of Dyers and Colourists. Colorants
include dyes and pigments and include those commonly used for
coloring textiles, paints, inks and inkjet inks. Some colorants
that can be utilized include carotenoids, arylide yellows,
diarylide yellows, -naphthols, naphthols, benzimidazolones, disazo
condensation pigments, pyrazolones, nickel azo yellow,
phthalocyanines, quinacridones, perylenes and perinones,
isoindolinone and isoindoline pigments, triarylcarbonium pigments,
diketopyrrolo-pyrrole pigments, thioindigoids. Cartenoids include
e.g., alpha-carotene, beta-carotene, gamma-carotene, lycopene,
lutein and astaxanthin Annatto extract, Dehydrated beets (beet
powder), Canthaxanthin, Caramel, Apo-8'-carotenal, Cochineal
extract, Carmine, Sodium copper chlorophyllin, Toasted partially
defatted cooked cottonseed flour, Ferrous gluconate, Ferrous
lactate, Grape color extract, Grape skin extract (enocianina),
Carrot oil, Paprika, Paprika oleoresin, Mica-based pearlescent
pigments, Riboflavin, Saffron, Titanium dioxide, carbon black,
self-dispersed carbon, Tomato lycopene extract; tomato lycopene
concentrate, Turmeric, Turmeric oleoresin, FD&C Blue No. 1,
FD&C Blue No. 2, FD&C Green No. 3, Orange B, Citrus Red No.
2, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5,
FD&C Yellow No. 6, Alumina (dried aluminum hydroxide), Calcium
carbonate, Potassium sodium copper chlorophyllin
(chlorophyllin-copper complex), Dihydroxyacetone, Bismuth
oxychloride, Ferric ammonium ferrocyanide, Ferric ferrocyanide,
Chromium hydroxide green, Chromium oxide greens, Guanine,
Pyrophyllite, Talc, Aluminum powder, Bronze powder, Copper powder,
Zinc oxide, D&C Blue No. 4, D&C Green No. 5, D&C Green
No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange
No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red
No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17,
D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C
Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No.
33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39,
D&C Violet No. 2, D&C Yellow No. 7, Ext. D&C Yellow No.
7, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No.
11, D&C Black No. 2, D&C Black No. 3 (3), D&C Brown No.
1, Ext. D&C, Chromium-cobalt-aluminum oxide, Ferric ammonium
citrate, Pyrogallol, Logwood extract,
1,4-Bis[(2-hydroxy-ethyl)amino]-9,10-anthracenedione
bis(2-propenoic)ester copolymers, 1,4-Bis
[(2-methylphenyl)amino]-9,10-anthracenedione,
1,4-Bis[4-(2-methacryloxyethyl) phenylamino] anthraquinone
copolymers, Carbazole violet, Chlorophyllin-copper complex,
Chromium-cobalt-aluminum oxide, C.I. Vat Orange 1,
2-[[2,5-Diethoxy-4-[(4-methylphenyl)thiol]
phenyl]azo]-1,3,5-benzenetriol, 16,23-Dihydrodinaphtho
[2,3-a:2',3'-i] naphth [2',3':6,7] indolo [2,3-c]
carbazole-5,10,15,17,22,24-hexone,
N,N'-(9,10-Dihydro-9,10-dioxo-1,5-anthracenediyl) bisbenzamide,
7,16-Dichloro-6,15-dihydro-5,9,14,18-anthrazinetetrone,
16,17-Dimethoxydinaphtho (1,2,3-cd:3',2',1'-lm)
perylene-5,10-dione, Poly(hydroxyethyl methacrylate)-dye copolymers
(3), Reactive Black 5, Reactive Blue 21, Reactive Orange 78,
Reactive Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, C.I.
Reactive Red 11, C.I. Reactive Yellow 86, C.I. Reactive Blue 163,
C.I. Reactive Red 180,
4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-on-
e (solvent Yellow 18), 6-Ethoxy-2-(6-ethoxy-3-oxobenzo[b]
thien-2(3H)-ylidene) benzo[b]thiophen-3(2H)-one, Phthalocyanine
green, Vinyl alcohol/methyl methacrylate-dye reaction products,
C.I. Reactive Red 180, C.I. Reactive Black 5, C.I. Reactive Orange
78, C.I. Reactive Yellow 15, C.I. Reactive Blue 21, Disodium
1-amino-4-[[4-[(2-bromo-1-oxoallyl)amino]-2-sulphonatophenyl]amino]-9,10--
dihydro-9,10-dioxoanthracene-2-sulphonate (Reactive Blue 69),
D&C Blue No. 9, [Phthalocyaninato(2-)] copper and mixtures of
these.
[0162] For example, a 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.RTM. mixer or an extruder,
e.g., a twin-screw extruder with counter-rotating screws. An
example of a Banbury.RTM. mixer is the F-Series Banbury.RTM. mixer,
manufactured by Farrel. An example of a twin-screw extruder is the
WP ZSK 50 MEGACOMPOUNDER.TM., manufactured by Coperion, Stuttgart,
Germany 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 trade name
POLYIFF.TM.. 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, juniper berry, lavender, lemon,
mandarin, marjoram, musk, myrrh, 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 U.S. Pat. No. 8,074,910 issued Dec. 13, 2011, the entire
disclosure of which incorporated herein by reference.
Uses of PLA And PLA Copolymers
[0163] Some uses of PLA and PLA containing materials include:
personal care items (e.g., tissues, towels, diapers), green
packaging, garden (compostable pots), consumer electronics (e.g.,
laptop and mobile phone casings), appliances, food packaging,
disposable packaging (e.g., food containers and drink bottles),
garbage bags (e.g., waste compostable bags), mulch films,
controlled release matrices and containers (e.g., for fertilizers,
pesticides, herbicides, nutrients, pharmaceuticals, flavoring
agents, foods), shopping bags, general purpose film, high heat
film, heat seal layer, surface coating, disposable tableware (e.g.,
plates, cups, forks, knives, spoons, sporks, bowls), automotive
parts (e.g., panels, fabrics, under hood covers), carpet fibers,
clothing fibers (e.g., for garments, sportswear, footwear),
biomedical applications (e.g., surgical sutures, implants,
scaffolding, drug delivery systems, dialysis equipment) and
engineering plastics.
[0164] Other uses/industrial sectors that can benefit from the use
of PLA and PLA derivatives (e.g., elastomers) include IT and
software, electronics, geoscience (e.g., oil and gas), engineering,
aerospace (e.g., arm rests, seats, panels), telecommunications
(e.g., headsets), chemical manufacturing, transportation such as
automotive (e.g., dashboards, panels, tires, wheels), materials and
steel, consumer packaged goods, wires and cables.
Other Advantages of PLA and PLA Copolymers
[0165] PLA is bio-based and can be composted, recycled, used as a
fuel (incinerated). Some of the degradation reactions include
thermal degradation, hydrolytic degradation and biotic
degradations.
[0166] PLA can be thermally degraded. For example, at high
temperatures (e.g., between about 200-300.degree. C., about
230-260.degree. C.). The reactions involved in the thermal
degradation of PLA can follow different mechanisms such as thermo
hydrolysis, zipper-like depolymerization (e.g., in the presence of
residual catalysts), thermo-oxidative degradation.
Transesterification reactions can also operate on the polymer
causing bond breaking and/or bond making.
[0167] PLA also can undergo hydrolytic degradation. Hydrolytic
degradation includes chain scission producing shorter polymers,
oligomers and eventually the monomer lactic acid can be released.
Hydrolysis can be associated with thermal and biotic degradation.
The process can be effected by various parameters such as the PLA
structure, its molecular weight and distribution, its morphology
(e.g., crystallinity), the shape of the sample (e.g., isolated thin
samples or comminuted samples can degrade faster), the thermal and
mechanical history (e.g., processing) and the hydrolysis conditions
(e.g., temperature, agitation, comminution). The hydrolysis of PLA
starts with a water uptake phase, followed by hydrolytic splitting
of the ester bonds. The amorphous parts of the polyesters can be
hydrolyzed faster than the crystalline regions because of the
higher water uptake and mobility of chain segments in these
regions. In a second stage, the crystalline regions of PLA are
hydrolyzed.
[0168] PLA can also undergo biotic degradation. This degradation
can occur for example, in a mammalian body, and has useful
implications for .degree. degradable stitching and can have
detrimental implications to other surgical implants. Enzymes, such
as proteinase K and pronase can be utilized.
[0169] During composting, PLA can go through several degradation
stages. For example, an initial stage can occur due to exposure to
moisture wherein the degradation is abiotic and the PLA degrades by
hydrolysis. This stage can be accelerated by the presence of acids
and bases and elevated temperatures. The first stage can lead to
embrittlement of the polymer which can facilitate the diffusion of
PLA out of the bulk polymers. The oligomers can then be attacked by
micro-organisms. Organisms can degrade the oligomers and lactic
acid, leading to CO.sub.2 and water. Time for this degradation is
on the order of about one to a few years depending on the factors
previously mentioned. The degradation time is several orders of
magnitude faster than typical petroleum based plastic such as
polyethylene (e.g., on the order of hundreds of years).
[0170] PLA can also be recycled. For example, the PLA can be
hydrolyzed to lactide acid, purified and re-polymerized. Unlike
other recyclable plastics such as PET and HDPE, PLA does not need
to be down-graded to make a product of diminished value (e.g., from
a bottle to decking or carpet). PLA can be in theory recycled
indefinitely. Optionally, PLA can be re-used and downgraded for
several generations and then converted to PLA and
re-polymerized.
[0171] PLA can also be used as a fuel, for example, for energy
production. PLA can have high heat content e.g., up to about 8400
BTU. Incineration of pure PLA only releases carbon dioxide and
water. Combinations with other ingredients typically amount to less
than 1 ppm of non PLA residuals (e.g., ash). Thus the combustion of
PLA is cleaner than other renewable fuels, e.g. wood. [00172] PLA
can have high gloss, high transparency, high clarity, high
stiffness, can be UV stable, non-allergenic, high flavor and aroma
barrier properties, easy to blend, easy to mold, easy to shape,
easy to emboss, easy to print on, lightweight, compostable.
[0172] PLA can also be printed on. For example, by lithographic,
ink-jet printing, laser printing, fixed-type printing, roller
printing. Some PLA can also be written on, for example, using a
pen.
[0173] Processing as described herein can also include irradiation.
For example, irradiation with between about 1 and 150 Mrad
radiation (e.g., for example, any range as described herein) can
improve the compostability and recyclability of PLA and PLA
containing materials.
Radiation Treatment
[0174] The feedstock (e.g., cellulosic, lignocellulosic, PLA, PLA
derivatives and combinations of these) can be treated with electron
bombardment to modify its structure, for example, to reduce its
recalcitrance or cross link the structures. Such treatment can, for
example, reduce the average molecular weight of the feedstock,
change the crystalline structure of the feedstock, and/or increase
the surface area and/or porosity of the feedstock. Alternatively
this treatment can produce radicals that can be sites for
cross-linking, grafting and/or functionalization.
[0175] Electron bombardment via an electron beam is generally
preferred, because it provides very high throughput. Accelerators
used to accelerate the particles can be electrostatic DC,
electrodynamic DC, RF linear, magnetic induction linear or
continuous wave. For example, cyclotron type accelerators are
available from IBA, Belgium, such as the RHODOTRON.TM. system,
while DC type accelerators are available from RDI, now IBA
Industrial, such as the DYNAMITRON.RTM.. Ions and ion accelerators
are discussed in Introductory Nuclear Physics, Kenneth S. Krane,
John Wiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997)
4, 177-206, Chu, William T., "Overview of Light-Ion Beam Therapy",
Columbus-Ohio, ICRU-IAEA Meeting, 18-20 Mar. 2006, Iwata, Y. et
al., "Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical
Accelerators", Proceedings of EPAC 2006, Edinburgh, Scotland, and
Leitner, C. M. et al., "Status of the Superconducting ECR Ion
Source Venus", Proceedings of EPAC 2000, Vienna, Austria.
[0176] Electron bombardment may be performed using an electron beam
device that has a nominal energy of less than 10 MeV, e.g., less
than 7 MeV, less than 5 MeV, or less than 2 MeV, e.g., from about
0.5 to 1.5 MeV, from about 0.8 to 1.8 MeV, or from about 0.7 to 1
MeV. In some implementations the nominal energy is about 500 to 800
keV.
[0177] The electron beam may have a relatively high total beam
power (the combined beam power of all accelerating heads, or, if
multiple accelerators are used, of all accelerators and all heads),
e.g., at least 25 kW, e.g., at least 30, 40, 50, 60, 65, 70, 80,
100, 125, or 150, 250, 300 kW. In some cases, the power is even as
high as 500 kW, 750 kW, or even 1000 kW or more. In some cases the
electron beam has a beam power of 1200 kW or more, e.g., 1400,
1600, 1800, or even 3000 kW. The electron beam may have a total
beam power of 25 to 3000 kW. Alternatively, the electron beam may
have a total beam power of 75 to 1500 kW. Optionally, the electron
beam may have a total beam power of 100 to 1000 kW. Alternatively,
the electron beam may have a total beam power of 100 to 400 kW.
[0178] This high total beam power is usually achieved by utilizing
multiple accelerating heads. For example, the electron beam device
may include two, four, or more accelerating heads. The use of
multiple heads, each of which has a relatively low beam power,
prevents excessive temperature rise in the material, thereby
preventing burning of the material, and also increases the
uniformity of the dose through the thickness of the layer of
material.
[0179] It is generally preferred that the bed of feedstock material
has a relatively uniform thickness. In some embodiments the
thickness is less than about 1 inch (e.g., less than about 0.75
inches, less than about 0.5 inches, less than about 0.25 inches,
less than about 0.1 inches, between about 0.1 and 1 inch, between
about 0.2 and 0.3 inches).
[0180] In some implementations, it is desirable to cool the
material during and between dosing the material with electron
bombardment. For example, the material can be cooled while it is
conveyed, for example, by a screw extruder, vibratory conveyor or
other conveying equipment. For example, cooling while conveying is
described International App. No. PCT/US2014/021609 filed Mar. 7,
2014 and International App. No. PCT/US2014/021632 filed Mar. 7,
2014, the entire descriptions of which are herein incorporated by
reference.
[0181] To reduce the energy required by the recalcitrance-reducing
process, it is desirable to treat the material as quickly as
possible. In general, the treatment be performed at a dose rate of
greater than about 0.25 Mrad per second, e.g., greater than about
0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about
20 Mrad per second, e.g., about 0.25 to 30 Mrad per second.
Alternately, the treatment is performed at a dose rate of 0.5 to 20
Mrad per second. Optionally, the treatment is performed at a dose
rate of 0.75 to 15 Mrad per second. Alternately, the treatment is
performed at a dose rate of 1 to 5 Mrad per second. Optionally, the
treatment is performed at a dose rate of 1-3 Mrad per second or
alternatively 1-2 Mrad per second. Higher dose rates allow a higher
throughput for a target (e.g., the desired) dose. Higher dose rates
generally require higher line speeds, to avoid thermal
decomposition of the material. In one implementation, the
accelerator is set for 3 MeV, 50 mA beam current, and the line
speed is 24 feet/minute, for a sample thickness of about 20 mm
(e.g., comminuted corn cob material with a bulk density of 0.5
g/cm.sup.3).
[0182] In some embodiments, electron bombardment is performed until
the material receives a total dose of at least 0.1 Mrad, 0.25 Mrad,
1 Mrad, 5 Mrad, e.g., at least 10, 20, 30 or at least 40 Mrad. In
some embodiments, the treatment is performed until the material
receives a dose of from about 10 Mrad to about 50 Mrad, e.g., from
about 20 Mrad to about 40 Mrad, or from about 25 Mrad to about 30
Mrad. In some implementations, a total dose of 25 to 35 Mrad is
preferred, applied ideally over a couple of seconds, e.g., at 5
Mrad/pass with each pass being applied for about one second.
Applying a dose of greater than 7 to 8 Mrad/pass can in some cases
cause thermal degradation of the feedstock material. Cooling can be
applied before, after, or during irradiation. For example, the
cooling methods, systems and equipment as described in the
following applications can be utilized: International App. No.
PCT/US2014/021609 filed Mar. 7, 2014, and International App. No.
PCT/US2013/064320 filed Oct. 10, 2013, the entire disclosures of
which are herein incorporated by reference.
[0183] Using multiple heads as discussed above, the material can be
treated in multiple passes, for example, two passes at 10 to 20
Mrad/pass, e.g., 12 to 18 Mrad/pass, separated by a few seconds of
cool-down, or three passes of 7 to 12 Mrad/pass, e.g., 5 to 20
Mrad/pass, 10 to 40 Mrad/pass, 9 to 11 Mrad/pass. As discussed
herein, treating the material with several relatively low doses,
rather than one high dose, tends to prevent overheating of the
material and also increases dose uniformity through the thickness
of the material. In some implementations, the material is stirred
or otherwise mixed during or after each pass and then smoothed into
a uniform layer again before the next pass, to further enhance
treatment uniformity.
[0184] In some embodiments, electrons are accelerated to, for
example, a speed of greater than 75 percent of the speed of light,
e.g., greater than 85, 90, 95, or 99 percent of the speed of
light.
[0185] In some embodiments, any processing described herein occurs
on feedstock material that remains dry as acquired or that has been
dried, e.g., using heat and/or reduced pressure. For example, in
some embodiments, the cellulosic and/or lignocellulosic material
has less than about 25 wt. % retained water, measured at 25.degree.
C. and at fifty percent relative humidity (e.g., less than about 20
wt. %, less than about 15 wt. %, less than about 14 wt. %, less
than about 13 wt. %, less than about 12 wt. %, less than about 10
wt. %, less than about 9 wt. %, less than about 8 wt. %, less than
about 7 wt. %, less than about 6 wt. %, less than about 5 wt. %,
less than about 4 wt. %, less than about 3 wt. %, less than about 2
wt. %, less than about 1 wt. %, less than about 0.5 wt. %, less
than about 15 wt. %.
[0186] In some embodiments, two or more electron sources are used,
such as two or more ionizing sources. For example, samples can be
treated, in any order, with a beam of electrons, followed by gamma
radiation and UV light having wavelengths from about 100 nm to
about 280 nm. In some embodiments, samples are treated with three
ionizing radiation sources, such as a beam of electrons, gamma
radiation, and energetic UV light. The biomass is conveyed through
the treatment zone where it can be bombarded with electrons.
[0187] It may be advantageous to repeat the treatment to more
thoroughly reduce the recalcitrance of the biomass and/or further
modify the biomass. In particular, the process parameters can be
adjusted after a first (e.g., second, third, fourth or more) pass
depending on the recalcitrance of the material. In some
embodiments, a conveyor can be used which includes a circular
system where the biomass is conveyed multiple times through the
various processes described above. In some other embodiments,
multiple treatment devices (e.g., electron beam generators) are
used to treat the biomass multiple (e.g., 2, 3, 4 or more) times.
In yet other embodiments, a single electron beam generator may be
the source of multiple beams (e.g., 2, 3, 4 or more beams) that can
be used for treatment of the biomass.
[0188] The effectiveness in changing the molecular/supermolecular
structure and/or reducing the recalcitrance of the
carbohydrate-containing biomass depends on the electron energy used
and the dose applied, while exposure time depends on the power and
dose. In some embodiments, the dose rate and total are adjusted so
as not to destroy (e.g., char or burn) the biomass material. For
example, the carbohydrates should not be damaged in the processing
so that they can be released from the biomass intact, e.g. as
monomeric sugars.
[0189] In some embodiments, the treatment (with any electron source
or a combination of sources) is performed until the material
receives a dose of at least about 0.05 Mrad, e.g., at least about
0.1, 0.25, 0.5, 0.75, 1.0, 2.5, 5.0, 7.5, 10.0, 15, 20, 25, 30, 40,
50, 60, 70, 80, 90, 100, 125, 150, 175, or 200 Mrad. In some
embodiments, the treatment is performed until the material receives
a dose of between 0.1-100 Mrad, 1-200, 5-200, 10-200, 5-150, 50-150
Mrad, 5-100, 5-50, 5-40, 10-50, 10-75, 15-50, 20-35 Mrad.
Radiation Opaque Materials
[0190] The invention can include processing the material in a vault
and/or bunker that is constructed using radiation opaque materials.
In some implementations, the radiation opaque materials are
selected to be capable of shielding the components from X-rays with
high energy (short wavelength), which can penetrate many materials.
One important factor in designing a radiation shielding enclosure
is the attenuation length of the materials used, which will
determine the required thickness for a particular material, blend
of materials, or layered structure. The attenuation length is the
penetration distance at which the radiation is reduced to
approximately 1/e (e=Euler's number) times that of the incident
radiation. Although virtually all materials are radiation opaque if
thick enough, materials containing a high compositional percentage
(e.g., density) of elements that have a high Z value (atomic
number) have a shorter radiation attenuation length and thus, if
such materials are used, a thinner, lighter shielding can be
provided. Examples of high Z value materials that are used in
radiation shielding are tantalum and lead. Another important
parameter in radiation shielding is the halving distance, which is
the thickness of a particular material that will reduce gamma ray
intensity by 50%. As an example for X-ray radiation with an energy
of 0.1 MeV the halving thickness is about 15.1 mm for concrete and
about 0.27 mm for lead, while with an X-ray energy of 1 MeV the
halving thickness for concrete is about 44.45 mm and for lead is
about 7.9 mm Radiation opaque materials can be materials that are
thick or thin so long as they can reduce the radiation that passes
through to the other side. Thus, if it is desired that a particular
enclosure have a low wall thickness, e.g., for light weight or due
to size constraints, the material chosen should have a sufficient Z
value and/or attenuation length so that its halving length is less
than or equal to the desired wall thickness of the enclosure.
[0191] In some cases, the radiation opaque material may be a
layered material, for example, having a layer of a higher Z value
material, to provide good shielding, and a layer of a lower Z value
material to provide other properties (e.g., structural integrity,
impact resistance, etc.). In some cases, the layered material may
be a "graded-Z" laminate, e.g., including a laminate in which the
layers provide a gradient from high-Z through successively lower-Z
elements. In some cases the radiation opaque materials can be
interlocking blocks, for example, lead and/or concrete blocks can
be supplied by NELCO Worldwide (Burlington, Mass.), and
reconfigurable vaults can be utilized as described in International
App. No. PCT/US2014/021629 filed on Mar. 7, 2014 the entire
disclosure of which is herein incorporated by reference.
[0192] A radiation opaque material can reduce the radiation passing
through a structure (e.g., a wall, door, ceiling, enclosure, a
series of these or combinations of these) formed of the material by
about at least about 10%, (e.g., at least about 20%, at least about
30%, at least about 40%, at least about 50%, at least about 60%, at
least about 70%, at least about 80%, at least about 90%, at least
about 95%, at least about 96%, at least about 97%, at least about
98%, at least about 99%, at least about 99.9%, at least about
99.99%, at least about 99.999%) as compared to the incident
radiation. Therefore, an enclosure made of a radiation opaque
material can reduce the exposure of equipment/system/components by
the same amount. Radiation opaque materials can include stainless
steel, metals with Z values above 25 (e.g., lead, iron), concrete,
dirt, sand and combinations thereof. Radiation opaque materials can
include a barrier in the direction of the incident radiation of at
least about 1 mm (e.g., 5 mm, 10 mm, 5 cm, 10 cm, 100 cm, 1 m, 10
m).
Electron Sources
[0193] Electrons interact via Coulomb scattering and bremsstrahlung
radiation produced by changes in the velocity of electrons.
Electrons may be produced by radioactive nuclei that undergo beta
decay, such as isotopes of iodine, cesium, technetium, and iridium.
Alternatively, an electron gun can be used as an electron source
via thermionic emission and accelerated through an accelerating
potential. An electron gun generates electrons, accelerates them
through a large potential (e.g., greater than about 500 thousand,
greater than about 1 million, greater than about 2 million, greater
than about 5 million, greater than about 6 million, greater than
about 7 million, greater than about 8 million, greater than about 9
million, or even greater than 10 million volts) and then scans them
magnetically in the x-y plane, where the electrons are initially
accelerated in the z direction down the tube and extracted through
a foil window. Scanning the electron beam is useful for increasing
the irradiation surface when irradiating materials, e.g., a
biomass, that is conveyed through the scanned beam. Scanning the
electron beam also distributes the thermal load homogenously on the
window and helps reduce the foil window rupture due to local
heating by the electron beam. Window foil rupture is a cause of
significant down-time due to subsequent necessary repairs and
re-starting the electron gun.
[0194] Various other irradiating devices may be used in the methods
disclosed herein, including field ionization sources, electrostatic
ion separators, field ionization generators, thermionic emission
sources, microwave discharge ion sources, recirculating or static
accelerators, dynamic linear accelerators, van de Graaff
accelerators, and folded tandem accelerators. Such devices are
disclosed, for example, in U.S. Pat. No. 7,931,784 to Medoff, the
complete disclosure of which is incorporated herein by
reference.
[0195] A beam of electrons can be used as the radiation source. A
beam of electrons has the advantages of high dose rates (e.g., 1,
5, or even 10 Mrad per second), high throughput, less containment,
and less confinement equipment. Electron beams can also have high
electrical efficiency (e.g., 80%), allowing for lower energy usage
relative to other radiation methods, which can translate into a
lower cost of operation and lower greenhouse gas emissions
corresponding to the smaller amount of energy used. Electron beams
can be generated, e.g., by electrostatic generators, cascade
generators, transformer generators, low energy accelerators with a
scanning system, low energy accelerators with a linear cathode,
linear accelerators, and pulsed accelerators.
[0196] Electrons can also be more efficient at causing changes in
the molecular structure of carbohydrate-containing materials, for
example, by the mechanism of chain scission. In addition, electrons
having energies of 0.5-10 MeV can penetrate low density materials,
such as the biomass materials described herein, e.g., materials
having a bulk density of less than 0.5 g/cm.sup.3, and a depth of
0.3-10 cm. Electrons as an ionizing radiation source can be useful,
e.g., for relatively thin piles, layers or beds of materials, e.g.,
less than about 0.5 inch, e.g., less than about 0.4 inch, 0.3 inch,
0.25 inch, or less than about 0.1 inch. In some embodiments, the
energy of each electron of the electron beam is from about 0.3 MeV
to about 2.0 MeV (million electron volts), e.g., from about 0.5 MeV
to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV. Methods
of irradiating materials are discussed in U.S. Pat. App. Pub.
2012/0100577 A1, filed Oct. 18, 2011, the entire disclosure of
which is herein incorporated by reference.
[0197] Electron beam irradiation devices may be procured
commercially from Ion Beam Applications, Louvain-la-Neuve, Belgium
or the Titan Corporation, San Diego, Calif. Typical electron
energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV.
Typical electron beam irradiation device power can be 1 KW, 5 KW,
10 KW, 20 KW, 50 KW, 60 KW, 70 KW, 80 KW, 90 KW, 100 KW, 125 KW,
150 KW, 175 KW, 200 KW, 250 KW, 300 KW, 350 KW, 400 KW, 450 KW, 500
KW, 600 KW, 700 KW, 800 KW, 900 KW or even 1000 KW.
[0198] Tradeoffs in considering electron beam irradiation device
power specifications include cost to operate, capital costs,
depreciation, and device footprint. Tradeoffs in considering
exposure dose levels of electron beam irradiation would be energy
costs and environment, safety, and health (ESH) concerns.
Typically, generators are housed in a vault, e.g., of lead or
concrete, especially for production from X-rays that are generated
in the process. Tradeoffs in considering electron energies include
energy costs.
[0199] The electron beam irradiation device can produce either a
fixed beam or a scanning beam. A scanning beam may be advantageous
with large scan sweep length and high scan speeds, as this would
effectively replace a large, fixed beam width. Further, available
sweep widths of 0.5 m, 1 m, 2 m or more are available. The scanning
beam is preferred in most embodiments described herein because of
the larger scan width and reduced possibility of local heating and
failure of the windows.
Electron Guns--Windows
[0200] The extraction system for an electron accelerator can
include two window foils. Window foils are described in
International App. No. PCT/US2013/064332 filed Oct. 10, 2013 the
complete disclosure of which is herein incorporated by reference.
The cooling gas in the two foil window extraction system can be a
pure gas or a mixture, for example, air, or a pure gas. In one
embodiment the gas is an inert gas such as nitrogen, argon, helium
and/or carbon dioxide. It is preferred to use a gas rather than a
liquid since energy losses to the electron beam are minimized
Mixtures of pure gas can also be used, either pre-mixed or mixed in
line prior to impinging on the windows or in the space between the
windows. The cooling gas can be cooled, for example, by using a
heat exchange system (e.g., a chiller) and/or by using boil off
from a condensed gas (e.g., liquid nitrogen, liquid helium).
[0201] When using an enclosure, the enclosed conveyor can also be
purged with an inert gas so as to maintain an atmosphere at a
reduced oxygen level. Keeping oxygen levels low avoids the
formation of ozone which in some instances is undesirable due to
its reactive and toxic nature. For example, the oxygen can be less
than about 20% (e.g., less than about 10%, less than about 1%, less
than about 0.1%, less than about 0.01%, or even less than about
0.001% oxygen). Purging can be done with an inert gas including,
but not limited to, nitrogen, argon, helium or carbon dioxide. This
can be supplied, for example, from a boil off of a liquid source
(e.g., liquid nitrogen or helium), generated or separated from air
in situ, or supplied from tanks. The inert gas can be recirculated
and any residual oxygen can be removed using a catalyst, such as a
copper catalyst bed. Alternatively, combinations of purging,
recirculating and oxygen removal can be done to keep the oxygen
levels low.
[0202] The enclosure can also be purged with a reactive gas that
can react with the biomass. This can be done before, during or
after the irradiation process. The reactive gas can be, but is not
limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons,
aromatic compounds, amides, peroxides, azides, halides, oxyhalides,
phosphides, phosphines, arsines, sulfides, thiols, boranes and/or
hydrides. The reactive gas can be activated in the enclosure, e.g.,
by irradiation (e.g., electron beam, UV irradiation, microwave
irradiation, heating, IR radiation), so that it reacts with the
biomass. The biomass itself can be activated, for example, by
irradiation. Preferably the biomass is activated by the electron
beam, to produce radicals which then react with the activated or
unactivated reactive gas, e.g., by radical coupling or
quenching.
[0203] Purging gases supplied to an enclosed conveyor can also be
cooled, for example, below about 25.degree. C., below about
0.degree. C., below about -40.degree. C., below about -80.degree.
C., below about -120.degree. C. For example, the gas can be boiled
off from a compressed gas such as liquid nitrogen or sublimed from
solid carbon dioxide. As an alternative example, the gas can be
cooled by a chiller or part of or the entire conveyor can be
cooled.
Heating and Throughput During Radiation Treatment
[0204] Several processes can occur in biomass when electrons from
an electron beam interact with matter in inelastic collisions. For
example, ionization of the material, chain scission of polymers in
the material, cross linking of polymers in the material, oxidation
of the material, generation of X-rays ("Bremsstrahlung") and
vibrational excitation of molecules (e.g. phonon generation).
Without being bound to a particular mechanism, the reduction in
recalcitrance can be due to several of these inelastic collision
effects, for example, ionization, chain scission of polymers,
oxidation and phonon generation. Some of the effects (e.g.,
especially X-ray generation), necessitate shielding and engineering
barriers, for example, enclosing the irradiation processes in a
concrete (or other radiation opaque material) vault. Another effect
of irradiation, vibrational excitation, is equivalent to heating up
the sample. Heating the sample by irradiation can help in
recalcitrance reduction, but excessive heating can destroy the
material, as will be explained below.
[0205] The adiabatic temperature rise (.DELTA.T) from adsorption of
ionizing radiation is given by the equation: .DELTA.T=D/Cp: where D
is the average dose in KGy, Cp is the heat capacity in J/g .degree.
C., and .DELTA.T is the change in temperature in .degree. C. A
typical dry biomass material will have a heat capacity close to 2.
Wet biomass will have a higher heat capacity dependent on the
amount of water since the heat capacity of water is very high (4.19
J/g .degree. C.). Metals have much lower heat capacities, for
example, 304 stainless steel has a heat capacity of 0.5 J/g
.degree. C. The temperature change due to the instant adsorption of
radiation in a biomass and stainless steel for various doses of
radiation is shown in Table 1.
TABLE-US-00002 TABLE 1 Calculated Temperature increase for biomass
and stainless steel. Dose (Mrad) Estimated Biomass .DELTA.T
(.degree. C.) Steel .DELTA.T (.degree. C.) 10 50 200 50 250,
Decomposition 1000 100 500, Decomposition 2000 150 750,
Decomposition 3000 200 1000, Decomposition 4000
[0206] High temperatures can destroy and or modify the biopolymers
in biomass so that the polymers (e.g., cellulose) are unsuitable
for further processing. A biomass subjected to high temperatures
can become dark, sticky and give off odors indicating
decomposition. The stickiness can even make the material hard to
convey. The odors can be unpleasant and be a safety issue. In fact,
keeping the biomass below about 200.degree. C. has been found to be
beneficial in the processes described herein (e.g., below about
190.degree. C., below about 180.degree. C., below about 170.degree.
C., below about 160.degree. C., below about 150.degree. C., below
about 140.degree. C., below about 130.degree. C., below about
120.degree. C., below about 110.degree. C., between about
60.degree. C. and 180.degree. C., between about 60.degree. C. and
160.degree. C., between about 60.degree. C. and 150.degree. C.,
between about 60.degree. C. and 140.degree. C., between about
60.degree. C. and 130.degree. C., between about 60.degree. C. and
120.degree. C., between about 80.degree. C. and 180.degree. C.,
between about 100.degree. C. and 180.degree. C., between about
120.degree. C. and 180.degree. C., between about 140.degree. C. and
180.degree. C., between about 160.degree. C. and 180.degree. C.,
between about 100.degree. C. and 140.degree. C., between about
80.degree. C. and 120.degree. C.).
[0207] It has been found that irradiation above about 10 Mrad is
desirable for the processes described herein (e.g., reduction of
recalcitrance). A high throughput is also desirable so that the
irradiation does not become a bottle neck in processing the
biomass. The treatment is governed by a Dose rate equation:
M=FP/D*time, where M is the mass of irradiated material (Kg), F is
the fraction of power that is adsorbed (unit less), P is the
emitted power (KW=Voltage in MeV*Current in mA), time is the
treatment time (sec) and D is the adsorbed dose (KGy). In an
exemplary process where the fraction of adsorbed power is fixed,
the Power emitted is constant and a set dosage is desired, the
throughput (e.g., M, the biomass processed) can be increased by
increasing the irradiation time. However, increasing the
irradiation time without allowing the material to cool, can
excessively heat the material as exemplified by the calculations
shown above. Since biomass has a low thermal conductivity (less
than about 0.1 Wm.sup.-1K.sup.-1), heat dissipation is slow,
unlike, for example, metals (greater than about 10
Wm.sup.-1K.sup.-1) which can dissipate energy quickly as long as
there is a heat sink to transfer the energy to.
Electron Guns--Beam Stops
[0208] In some embodiments the systems and methods include a beam
stop (e.g., a shutter). For example, the beam stop can be used to
quickly stop or reduce the irradiation of material without powering
down the electron beam device. Alternatively the beam stop can be
used while powering up the electron beam, e.g., the beam stop can
stop the electron beam until a beam current of a desired level is
achieved. The beam stop can be placed between the primary foil
window and a secondary foil window. For example, the beam stop can
be mounted so that it is movable, that is, so that it can be moved
into and out of the beam path. Even partial coverage of the beam
can be used, for example, to control the dose of irradiation. The
beam stop can be mounted to the floor, to a conveyor for the
biomass, to a wall, to the radiation device (e.g., at the scan
horn), or to any structural support. Preferably, the beam stop is
fixed in relation to the scan horn so that the beam can be
effectively controlled by the beam stop. The beam stop can
incorporate a hinge, a rail, wheels, slots, or other means allowing
for its operation in moving into and out of the beam. The beam stop
can be made of any material that will stop at least 5% of the
electrons, e.g., at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, at
least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or
even about 100% of the electrons.
[0209] The beam stop can be made of a metal including, but not
limited to, stainless steel, lead, iron, molybdenum, silver, gold,
titanium, aluminum, tin, or alloys of these, or laminates (layered
materials) made with such metals (e.g., metal-coated ceramic,
metal-coated polymer, metal-coated composite, multilayered metal
materials).
[0210] The beam stop can be cooled, for example, with a cooling
fluid such as an aqueous solution or a gas. The beam stop can be
partially or completely hollow, for example, with cavities.
Interior spaces of the beam stop can be used for cooling fluids and
gases. The beam stop can be of any shape, including flat, curved,
round, oval, square, rectangular, beveled and wedged shapes.
[0211] The beam stop can have perforations so as to allow some
electrons through, thus controlling (e.g., reducing) the levels of
radiation across the whole area of the window, or in specific
regions of the window. The beam stop can be a mesh formed, for
example, from fibers or wires. Multiple beam stops can be used,
together or independently, to control the irradiation. The beam
stop can be remotely controlled, e.g., by radio signal or hard
wired to a motor for moving the beam into or out of position.
Biomass Materials
[0212] Lignocellulosic materials include, but are not limited to,
wood (e.g., softwood, Pine softwood, Softwood, Softwood barks,
Softwood stems, Spruce softwood, Hardwood, Willow Hardwood, aspen
hardwood, Birch Hardwood, Hardwood barks, Hardwood stems, pine
cones, pine needles), particle board, chemical pulps, mechanical
pulps, paper, waste paper, forestry wastes (e.g., sawdust, aspen
wood, wood chips, leaves), grasses, (e.g., switchgrass, miscanthus,
cord grass, reed canary grass, Coastal Bermuda grass), grain
residues, (e.g., rice hulls, oat hulls, wheat chaff, barley hulls),
agricultural waste (e.g., silage, canola straw, wheat straw, barley
straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal,
abaca, corn cobs, corn stover, soybean stover, corn fiber, alfalfa,
hay, coconut hair, nut shells, palm and coconut oil byproducts),
cotton, Cotton seed hairs, flax, sugar processing residues (e.g.,
bagasse, beet pulp, agave bagasse), algae, seaweed, manure (e.g.,
Solid cattle manure, Swine waste), sewage, carrot processing waste,
molasses spent wash, alfalfa biver and mixtures of any of
these.
[0213] In some cases, the lignocellulosic material includes
corncobs. Ground or hammermilled corncobs can be spread in a layer
of relatively uniform thickness for irradiation, and after
irradiation are easy to disperse in the medium for further
processing. To facilitate harvest and collection, in some cases the
entire corn plant is used, including the corn stalk, corn kernels,
and in some cases even the root system of the plant.
[0214] Advantageously, no additional nutrients (other than a
nitrogen source, e.g., urea or ammonia) are required during
fermentation of corncobs or cellulosic or lignocellulosic materials
containing significant amounts of corncobs.
[0215] Corncobs, before and after comminution, are also easier to
convey and disperse, and have a lesser tendency to form explosive
mixtures in air than other cellulosic or lignocellulosic materials
such as hay and grasses.
[0216] Cellulosic materials include, for example, paper, paper
products, paper waste, paper pulp, pigmented papers, loaded papers,
coated papers, filled papers, magazines, printed matter (e.g.,
books, catalogs, manuals, labels, calendars, greeting cards,
brochures, prospectuses, newsprint), printer paper, polycoated
paper, card stock, cardboard, paperboard, materials having a high
a-cellulose content such as cotton, and mixtures of any of these.
For example, paper products as described in U.S. application Ser.
No. 13/396,365 ("Magazine Feedstocks" by Medoff et al., filed Feb.
14, 2012), the full disclosure of which is incorporated herein by
reference.
[0217] Cellulosic materials can also include lignocellulosic
materials which have been partially or fully de-lignified.
[0218] In some instances other biomass materials can be utilized,
for example, starchy materials. Starchy materials include starch
itself, e.g., corn starch, wheat starch, potato starch or rice
starch, a derivative of starch, or a material that includes starch,
such as an edible food product or a crop. For example, the starchy
material can be arracacha, buckwheat, banana, barley, cassava,
kudzu, ocra, sago, sorghum, regular household potatoes, sweet
potato, taro, yams, or one or more beans, such as favas, lentils or
peas. Blends of any two or more starchy materials are also starchy
materials. Mixtures of starchy, cellulosic and or lignocellulosic
materials can also be used. For example, a biomass can be an entire
plant, a part of a plant or different parts of a plant, e.g., a
wheat plant, cotton plant, a corn plant, rice plant or a tree. The
starchy materials can be treated by any of the methods described
herein.
[0219] Microbial materials include, but are not limited to, any
naturally occurring or genetically modified microorganism or
organism that contains or is capable of providing a source of
carbohydrates (e.g., cellulose), for example, protists, e.g.,
animal protists (e.g., protozoa such as flagellates, amoeboids,
ciliates, and sporozoa) and plant protists (e.g., algae such
alveolates, chlorarachniophytes, cryptomonads, euglenids,
glaucophytes, haptophytes, red algae, stramenopiles, and
viridiplantae). Other examples include seaweed, plankton (e.g.,
macroplankton, mesoplankton, microplankton, nanoplankton,
picoplankton, and femtoplankton), phytoplankton, bacteria (e.g.,
gram positive bacteria, gram negative bacteria, and extremophiles),
yeast and/or mixtures of these. In some instances, microbial
biomass can be obtained from natural sources, e.g., the ocean,
lakes, bodies of water, e.g., salt water or fresh water, or on
land. Alternatively or in addition, microbial biomass can be
obtained from culture systems, e.g., large scale dry and wet
culture and fermentation systems.
[0220] In other embodiments, the biomass materials, such as
cellulosic, starchy and lignocellulosic feedstock materials, can be
obtained from transgenic microorganisms and plants that have been
modified with respect to a wild type variety. Such modifications
may be, for example, through the iterative steps of selection and
breeding to obtain desired traits in a plant. Furthermore, the
plants can have had genetic material removed, modified, silenced
and/or added with respect to the wild type variety. For example,
genetically modified plants can be produced by recombinant DNA
methods, where genetic modifications include introducing or
modifying specific genes from parental varieties, or, for example,
by using transgenic breeding wherein a specific gene or genes are
introduced to a plant from a different species of plant and/or
bacteria. Another way to create genetic variation is through
mutation breeding wherein new alleles are artificially created from
endogenous genes. The artificial genes can be created by a variety
of ways including treating the plant or seeds with, for example,
chemical mutagens (e.g., using alkylating agents, epoxides,
alkaloids, peroxides, formaldehyde), irradiation (e.g., X-rays,
gamma rays, neutrons, beta particles, alpha particles, protons,
deuterons, UV radiation) and temperature shocking or other external
stressing and subsequent selection techniques. Other methods of
providing modified genes is through error prone PCR and DNA
shuffling followed by insertion of the desired modified DNA into
the desired plant or seed. Methods of introducing the desired
genetic variation in the seed or plant include, for example, the
use of a bacterial carrier, biolistics, calcium phosphate
precipitation, electroporation, gene splicing, gene silencing,
lipofection, microinjection and viral carriers. Additional
genetically modified materials have been described in U.S.
application Ser. No. 13/396,369 filed Feb. 14, 2012 the full
disclosure of which is incorporated herein by reference. Any of the
methods described herein can be practiced with mixtures of any
biomass materials described herein.
Biomass Material Preparation--Mechanical Treatments
[0221] The biomass can be in a dry form, for example, with less
than about 35% moisture content (e.g., less than about 20%, less
than about 15%, less than about 10% less than about 5%, less than
about 4%, less than about 3%, less than about 2% or even less than
about 1%). The biomass can also be delivered in a wet state, for
example, as a wet solid, a slurry or a suspension with at least
about 10 wt. % solids (e.g., at least about 20 wt. %, at least
about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %,
at least about 60 wt. %, at least about 70 wt. %).
[0222] The processes disclosed herein can utilize low bulk density
materials, for example, cellulosic or lignocellulosic feedstocks
that have been physically pretreated to have a bulk density of less
than about 0.75 g/cm.sup.3, e.g., less than about 0.7, 0.65, 0.60,
0.50, 0.35, 0.25, 0.20, 0.15, 0.10, 0.05 or less, e.g., less than
about 0.025 g/cm.sup.3. Bulk density is determined using ASTM
D1895B. Briefly, the method involves filling a measuring cylinder
of known volume with a sample and obtaining a weight of the sample.
The bulk density is calculated by dividing the weight of the sample
in grams by the known volume of the cylinder in cubic centimeters.
If desired, low bulk density materials can be densified, for
example, by methods described in U.S. Pat. No. 7,971,809 to Medoff,
the full disclosure of which is hereby incorporated by
reference.
[0223] In some cases, the pre-treatment processing includes
screening of the biomass material. Screening can be through a mesh
or perforated plate with a desired opening size, for example, less
than about 6.35 mm (1/4 inch, 0.25 inch), (e.g., less than about
3.18 mm (1/8 inch, 0.125 inch), less than about 1.59 mm ( 1/16
inch, 0.0625 inch), is less than about 0.79 mm ( 1/32 inch, 0.03125
inch), e.g., less than about 0.51 mm ( 1/50 inch, 0.02000 inch),
less than about 0.40 mm ( 1/64 inch, 0.015625 inch), less than
about 0.23 mm (0.009 inch), less than about 0.20 mm ( 1/128 inch,
0.0078125 inch), less than about 0.18 mm (0.007 inch), less than
about 0.13 mm (0.005 inch), or even less than about 0.10 mm ( 1/256
inch, 0.00390625 inch)). In one configuration the desired biomass
falls through the perforations or screen and thus biomass larger
than the perforations or screen are not irradiated. These larger
materials can be re-processed, for example, by comminuting, or they
can simply be removed from processing. In another configuration,
material that is larger than the perforations is irradiated and the
smaller material is removed by the screening process or recycled.
In this kind of a configuration, the conveyor itself (for example,
a part of the conveyor) can be perforated or made with a mesh. For
example, in one particular embodiment the biomass material may be
wet and the perforations or mesh allow water to drain away from the
biomass before irradiation.
[0224] Screening of material can also be by a manual method, for
example, by an operator or mechanoid (e.g., a robot equipped with a
color, reflectivity or other sensor) that removes unwanted
material. Screening can also be by magnetic screening wherein a
magnet is disposed near the conveyed material and the magnetic
material is removed magnetically.
[0225] Optional pre-treatment processing can include heating the
material. For example, a portion of the conveyor can be sent
through a heated zone. The heated zone can be created, for example,
by IR radiation, microwaves, combustion (e.g., gas, coal, oil,
biomass), resistive heating and/or inductive coils. The heat can be
applied from at least one side or more than one side, can be
continuous or periodic and can be for only a portion of the
material or all the material. For example, a portion of the
conveying trough can be heated by use of a heating jacket. Heating
can be, for example, for the purpose of drying the material. In the
case of drying the material, this can also be facilitated, with or
without heating, by the movement of a gas (e.g., air, oxygen,
nitrogen, He, CO.sub.2, Argon) over and/or through the biomass as
it is being conveyed.
[0226] Optionally, pre-treatment processing can include cooling the
material. Cooling material is described in U.S. Pat. No. 7,900,857
to Medoff, the disclosure of which in incorporated herein by
reference. For example, cooling can be by supplying a cooling
fluid, for example, water (e.g., with glycerol), or nitrogen (e.g.,
liquid nitrogen) to the bottom of the conveying trough.
Alternatively, a cooling gas, for example, chilled nitrogen can be
blown over the biomass materials or under the conveying system.
[0227] Another optional pre-treatment processing method can include
adding a material to the biomass. The additional material can be
added by, for example, by showering, sprinkling and or pouring the
material onto the biomass as it is conveyed. Materials that can be
added include, for example, metals, ceramics and/or ions as
described in U.S. Pat. App. Pub. 2010/0105119 A1 (filed Oct. 26,
2009) and U.S. Pat. App. Pub. 2010/0159569 A1 (filed Dec. 16,
2009), the entire disclosures of which are incorporated herein by
reference. Optional materials that can be added include acids and
bases. Other materials that can be added are oxidants (e.g.,
peroxides, chlorates), polymers, polymerizable monomers (e.g.,
containing unsaturated bonds), water, catalysts, enzymes and/or
organisms. Materials can be added, for example, in pure form, as a
solution in a solvent (e.g., water or an organic solvent) and/or as
a solution. In some cases the solvent is volatile and can be made
to evaporate e.g., by heating and/or blowing gas as previously
described. The added material may form a uniform coating on the
biomass or be a homogeneous mixture of different components (e.g.,
biomass and additional material). The added material can modulate
the subsequent irradiation step by increasing the efficiency of the
irradiation, damping the irradiation or changing the effect of the
irradiation (e.g., from electron beams to X-rays or heat). The
method may have no impact on the irradiation but may be useful for
further downstream processing. The added material may help in
conveying the material, for example, by lowering dust levels.
[0228] Biomass can be delivered to the conveyor (e.g., the
vibratory conveyors used in the vaults herein described) by a belt
conveyor, a pneumatic conveyor, a screw conveyor, a hopper, a pipe,
manually or by a combination of these. The biomass can, for
example, be dropped, poured and/or placed onto the conveyor by any
of these methods. In some embodiments the material is delivered to
the conveyor using an enclosed material distribution system to help
maintain a low oxygen atmosphere and/or control dust and fines.
Lofted or air suspended biomass fines and dust are undesirable
because these can form an explosion hazard or damage the window
foils of an electron gun (if such a device is used for treating the
material).
[0229] The material can be leveled to form a uniform thickness
between about 0.0312 and 5 inches (e.g., between about 0.0625 and
2.000 inches, between about 0.125 and 1 inches, between about 0.125
and 0.5 inches, between about 0.3 and 0.9 inches, between about 0.2
and 0.5 inches between about 0.25 and 1.0 inches, between about
0.25 and 0.5 inches, 0.100+/-0.025 inches, 0.150+/-0.025 inches,
0.200+/-0.025 inches, 0.250+/-0.025 inches, 0.300+/-0.025 inches,
0.350+/-0.025 inches, 0.400+/-0.025 inches, 0.450+/-0.025 inches,
0.500+/-0.025 inches, 0.550+/-0.025 inches, 0.600+/-0.025 inches,
0.700+/-0.025 inches, 0.750+/-0.025 inches, 0.800+/-0.025 inches,
0.850+/-0.025 inches, 0.900+/-0.025 inches, 0.900+/-0.025
inches.
[0230] Generally, it is preferred to convey the material as quickly
as possible through the electron beam to maximize throughput. For
example, the material can be conveyed at rates of at least 1
ft./min, e.g., at least 2 ft./min, at least 3 ft./min, at least 4
ft./min, at least 5 ft./min, at least 10 ft./min, at least 15
ft./min, 20, 25, 30, 35, 40, 45, 50 ft./min. The rate of conveying
is related to the beam current, for example, for a 1/4 inch thick
biomass and 100 mA, the conveyor can move at about 20 ft./min to
provide a useful irradiation dosage, at 50 mA the conveyor can move
at about 10 ft./min to provide approximately the same irradiation
dosage.
[0231] After the biomass material has been conveyed through the
radiation zone, optional post-treatment processing can be done. The
optional post-treatment processing can, for example, be a process
described with respect to the pre-irradiation processing. For
example, the biomass can be screened, heated, cooled, and/or
combined with additives. Uniquely to post-irradiation, quenching of
the radicals can occur, for example, quenching of radicals by the
addition of fluids or gases (e.g., oxygen, nitrous oxide, ammonia,
liquids), using pressure, heat, and/or the addition of radical
scavengers. For example, the biomass can be conveyed out of the
enclosed conveyor and exposed to a gas (e.g., oxygen) where it is
quenched, forming carboxylated groups. In one embodiment, the
biomass is exposed during irradiation to the reactive gas or fluid.
Quenching of biomass that has been irradiated is described in U.S.
Pat. No. 8,083,906 to Medoff, the entire disclosure of which is
incorporate herein by reference.
[0232] If desired, one or more mechanical treatments can be used in
addition to irradiation to further reduce the recalcitrance of the
carbohydrate-containing material. These processes can be applied
before, during and or after irradiation.
[0233] In some cases, the mechanical treatment may include an
initial preparation of the feedstock as received, e.g., size
reduction of materials, such as by comminution, e.g., cutting,
grinding, shearing, pulverizing or chopping. For example, in some
cases, loose feedstock (e.g., recycled paper, starchy materials, or
switchgrass) is prepared by shearing or shredding. Mechanical
treatment may reduce the bulk density of the
carbohydrate-containing material, increase the surface area of the
carbohydrate-containing material and/or decrease one or more
dimensions of the carbohydrate-containing material.
[0234] Alternatively, or in addition, the feedstock material can be
treated with another treatment, for example, chemical treatments,
such as with an acid (HCl, H.sub.2SO.sub.4, H.sub.3PO.sub.4), a
base (e.g., KOH and NaOH), a chemical oxidant (e.g., peroxides,
chlorates, ozone), irradiation, steam explosion, pyrolysis,
sonication, oxidation, chemical treatment. The treatments can be in
any order and in any sequence and combinations. For example, the
feedstock material can first be physically treated by one or more
treatment methods, e.g., chemical treatment including and in
combination with acid hydrolysis (e.g., utilizing HCl,
H.sub.2SO.sub.4, H.sub.3PO.sub.4), radiation, sonication,
oxidation, pyrolysis or steam explosion, and then mechanically
treated. This sequence can be advantageous since materials treated
by one or more of the other treatments, e.g., irradiation or
pyrolysis, tend to be more brittle and, therefore, it may be easier
to further change the structure of the material by mechanical
treatment. As another example, a feedstock material can be conveyed
through ionizing radiation using a conveyor as described herein and
then mechanically treated. Chemical treatment can remove some or
all of the lignin (for example, chemical pulping) and can partially
or completely hydrolyze the material. The methods also can be used
with pre-hydrolyzed material. The methods also can be used with
material that has not been pre hydrolyzed The methods can be used
with mixtures of hydrolyzed and non-hydrolyzed materials, for
example, with about 50% or more non-hydrolyzed material, with about
60% or more non-hydrolyzed material, with about 70% or more
non-hydrolyzed material, with about 80% or more non-hydrolyzed
material or even with 90% or more non-hydrolyzed material.
[0235] In addition to size reduction, which can be performed
initially and/or later in processing, mechanical treatment can also
be advantageous for "opening up," "stressing," breaking or
shattering the carbohydrate-containing materials, making the
cellulose of the materials more susceptible to chain scission
and/or disruption of crystalline structure during the physical
treatment.
[0236] Methods of mechanically treating the carbohydrate-containing
material include, for example, milling or grinding Milling may be
performed using, for example, a hammer mill, ball mill, colloid
mill, conical or cone mill, disk mill, edge mill, Wiley mill, grist
mill or other mill. Grinding may be performed using, for example, a
cutting/impact type grinder. Some exemplary grinders include stone
grinders, pin grinders, coffee grinders, and burr grinders.
Grinding or milling may be provided, for example, by a
reciprocating pin or other element, as is the case in a pin mill.
Other mechanical treatment methods include mechanical ripping or
tearing, other methods that apply pressure to the fibers, and air
attrition milling Suitable mechanical treatments further include
any other technique that continues the disruption of the internal
structure of the material that was initiated by the previous
processing steps.
[0237] Mechanical feed preparation systems can be configured to
produce streams with specific characteristics such as, for example,
specific maximum sizes, specific length-to-width, or specific
surface areas ratios. Physical preparation can increase the rate of
reactions, improve the movement of material on a conveyor, improve
the irradiation profile of the material, improve the radiation
uniformity of the material, or reduce the processing time required
by opening up the materials and making them more accessible to
processes and/or reagents, such as reagents in a solution.
[0238] The bulk density of feedstocks can be controlled (e.g.,
increased). In some situations, it can be desirable to prepare a
low bulk density material, e.g., by densifying the material (e.g.,
densification can make it easier and less costly to transport to
another site) and then reverting the material to a lower bulk
density state (e.g., after transport). The material can be
densified, for example, from less than about 0.2 g/cc to more than
about 0.9 g/cc (e.g., less than about 0.3 to more than about 0.5
g/cc, less than about 0.3 to more than about 0.9 g/cc, less than
about 0.5 to more than about 0.9 g/cc, less than about 0.3 to more
than about 0.8 g/cc, less than about 0.2 to more than about 0.5
g/cc). For example, the material can be densified by the methods
and equipment disclosed in U.S. Pat. No. 7,932,065 to Medoff and
International Publication No. WO 2008/073186 (which was filed Oct.
26, 2007, was published in English, and which designated the United
States), the full disclosures of which are incorporated herein by
reference. Densified materials can be processed by any of the
methods described herein, or any material processed by any of the
methods described herein can be subsequently densified.
[0239] In some embodiments, the material to be processed is in the
form of a fibrous material that includes fibers provided by
shearing a fiber source. For example, the shearing can be performed
with a rotary knife cutter.
[0240] For example, a fiber source, e.g., that is recalcitrant or
that has had its recalcitrance level reduced, can be sheared, e.g.,
in a rotary knife cutter, to provide a first fibrous material. The
first fibrous material is passed through a first screen, e.g.,
having an average opening size of 1.59 mm or less ( 1/16 inch,
0.0625 inch), provide a second fibrous material. If desired, the
fiber source can be cut prior to the shearing, e.g., with a
shredder. For example, when a paper is used as the fiber source,
the paper can be first cut into strips that are, e.g., 1/4-to
1/2-inch wide, using a shredder, e.g., a counter-rotating screw
shredder, such as those manufactured by Munson (Utica, N.Y.). As an
alternative to shredding, the paper can be reduced in size by
cutting to a desired size using a guillotine cutter. For example,
the guillotine cutter can be used to cut the paper into sheets that
are, e.g., 10 inches wide by 12 inches long.
[0241] In some embodiments, the shearing of the fiber source and
the passing of the resulting first fibrous material through a first
screen are performed concurrently. The shearing and the passing can
also be performed in a batch-type process.
[0242] For example, a rotary knife cutter can be used to
concurrently shear the fiber source and screen the first fibrous
material. A rotary knife cutter includes a hopper that can be
loaded with a shredded fiber source prepared by shredding a fiber
source.
[0243] In some implementations, the feedstock is physically treated
prior to saccharification and/or fermentation. Physical treatment
processes can include one or more of any of those described herein,
such as mechanical treatment, chemical treatment, irradiation,
sonication, oxidation, pyrolysis or steam explosion. Treatment
methods can be used in combinations of two, three, four, or even
all of these technologies (in any order). When more than one
treatment method is used, the methods can be applied at the same
time or at different times. Other processes that change a molecular
structure of a biomass feedstock may also be used, alone or in
combination with the processes disclosed herein.
[0244] Mechanical treatments that may be used, and the
characteristics of the mechanically treated carbohydrate-containing
materials, are described in further detail in U.S. Pat. App. Pub.
2012/0100577 A1, filed Oct. 18, 2011, the full disclosure of which
is hereby incorporated herein by reference.
[0245] The mechanical treatments described herein can also be
applied to processing of PLA and PLA based materials.
Sonication, Pyrolysis, Oxidation, Steam Explosion
[0246] If desired, one or more sonication, pyrolysis, oxidative, or
steam explosion processes can be used instead of or in addition to
irradiation to reduce or further reduce the recalcitrance of the
carbohydrate-containing material or process PLA and/or PLA based
materials. For example, these processes can be applied before,
during and or after irradiation. These processes are described in
detail in U.S. Pat. No. 7,932,065 to Medoff, the full disclosure of
which is incorporated herein by reference.
Heat Treatment of Biomass
[0247] Alternately, or in addition to the biomass may be heat
treated for up to twelve hours at temperatures ranging from about
90.degree. C. to about 160.degree. C. Optionally, this heat
treatment step is performed after biomass has been irradiated with
an electron beam. The amount of time for the heat treatment is up
to 9 hours, alternately up to 6 hours, optionally up to 4 hours and
further up to about 2 hours. The treatment time can be up to as
little as 30 minutes when the mass may be effectively heated.
[0248] The heat treatment can be performed 90.degree. C. to about
160.degree. C. or, optionally, at 100 to 150 or, alternatively, at
120 to 140.degree. C. The biomass is suspended in water such that
the biomass content is 10 to 75 wt. % in water. In the case of the
biomass being the irradiated biomass water is added and the heat
treatment performed.
[0249] The heat treatment is performed in an aqueous suspension or
mixture of the biomass. The amount of biomass is 10 to 90 wt. % of
the total mixture, alternatively 20 to 70 wt. % or optionally 25 to
50 wt. %. The irradiated biomass may have minimal water content so
water must be added prior to the heat treatment.
[0250] Since at temperatures above 100.degree. C. there will be
pressure vessel required to accommodate the pressure due to the
vaporized of water. The process for the heat treatment may be
batch, continuous, semi-continuous or other reactor configurations.
The continuous reactor configuration may be a tubular reactor and
may include device(s) within the tube which will facilitate heat
transfer and mixing/suspension of the biomass. These tubular
devices may include a one or more static mixers. The heat may also
be put into the system by direct injection of steam.
Use of Treated Biomass Material
[0251] Using the methods described herein, a starting biomass
material (e.g., plant biomass, animal biomass, paper, and municipal
waste biomass) can be used as feedstock to produce useful
intermediates and products such as organic acids, salts of organic
acids, hydroxy-carboxylic acids, PLA, acid anhydrides, esters of
organic acids and fuels, e.g., fuels for internal combustion
engines or feedstocks for fuel cells. Systems and processes are
described herein that can use as feedstock cellulosic and/or
lignocellulosic materials that are readily available, but often can
be difficult to process, e.g., municipal waste streams and waste
paper streams, such as streams that include newspaper, kraft paper,
corrugated paper or mixtures of these.
[0252] In order to convert the feedstock to a form that can be
readily processed, the glucan- or xylan-containing cellulose in the
feedstock can be hydrolyzed to low molecular weight carbohydrates,
such as sugars, by a saccharifying agent, e.g., an enzyme or acid,
a process referred to as saccharification. The low molecular weight
carbohydrates can then be used, for example, in an existing
manufacturing plant, such as a single cell protein plant, an enzyme
manufacturing plant, or a fuel plant, e.g., an ethanol
manufacturing facility.
[0253] The feedstock can be hydrolyzed using an enzyme, e.g., by
combining the materials and the enzyme in a solvent, e.g., in an
aqueous solution.
[0254] Alternatively, the enzymes can be supplied by organisms that
break down biomass, such as the cellulose and/or the lignin
portions of the biomass, contain or manufacture various
cellulolytic enzymes (cellulases), ligninases or various small
molecule biomass-degrading metabolites. These enzymes may be a
complex of enzymes that act synergistically to degrade crystalline
cellulose or the lignin portions of biomass. Examples of
cellulolytic enzymes include: endoglucanases, cellobiohydrolases,
and cellobiases (beta-glucosidases).
[0255] During saccharification a cellulosic substrate can be
initially hydrolyzed by endoglucanases at random locations
producing oligomeric intermediates. These intermediates are then
substrates for exo-splitting glucanases such as cellobiohydrolase
to produce cellobiose from the ends of the cellulose polymer.
Cellobiose is a water-soluble 1,4-linked dimer of glucose. Finally,
cellobiase cleaves cellobiose to yield glucose. The efficiency
(e.g., time to hydrolyze and/or completeness of hydrolysis) of this
process depends on the recalcitrance of the cellulosic
material.
Intermediates and Products
[0256] Using the processes described herein, the biomass material
can be converted to one or more products, such as energy, fuels,
foods and materials. Specific examples of products include, but are
not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinose,
mannose, galactose, fructose, disaccharides, oligosaccharides and
polysaccharides), alcohols (e.g., monohydric alcohols or dihydric
alcohols, such as ethanol, n-propanol, isobutanol, sec-butanol,
tert-butanol or n-butanol), hydrated or hydrous alcohols (e.g.,
containing greater than 10%, 20%, 30% or even greater than 40%
water), biodiesel, organic acids, hydrocarbons (e.g., methane,
ethane, propane, isobutene, pentane, n-hexane, biodiesel,
bio-gasoline and mixtures thereof), co-products (e.g., proteins,
such as cellulolytic proteins (enzymes) or single cell proteins),
and mixtures of any of these in any combination or relative
concentration, and optionally in combination with any additives
(e.g., fuel additives). Other examples include carboxylic acids,
salts of a carboxylic acid, a mixture of carboxylic acids and salts
of carboxylic acids and esters of carboxylic acids (e.g., methyl,
ethyl and n-propyl esters), ketones (e.g., acetone), aldehydes
(e.g., acetaldehyde), alpha and beta unsaturated acids (e.g.,
acrylic acid) and olefins (e.g., ethylene). Other alcohols and
alcohol derivatives include propanol, propylene glycol,
1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g., erythritol,
glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol,
dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and
other polyols), and methyl or ethyl esters of any of these
alcohols. Other products include methyl acrylate, methyl
methacrylate, lactic acid, PLA, citric acid, formic acid, acetic
acid, propionic acid, butyric acid, succinic acid, valeric acid,
caproic acid, 3-hydroxypropionic acid, palmitic acid, stearic acid,
oxalic acid, malonic acid, glutaric acid, oleic acid, linoleic
acid, glycolic acid, gamma-hydroxybutyric acid, and mixtures
thereof, salts of any of these acids, mixtures of any of the acids
and their respective salts.
[0257] Any combination of the above products with each other,
and/or of the above products with other products, which other
products may be made by the processes described herein or
otherwise, may be packaged together and sold as products. The
products may be combined, e.g., mixed, blended or co-dissolved, or
may simply be packaged or sold together.
[0258] Any of the products or combinations of products described
herein may be sanitized or sterilized prior to selling the
products, e.g., after purification or isolation or even after
packaging, to neutralize one or more potentially undesirable
contaminants that could be present in the product(s). Such
sanitation can be done with electron bombardment, for example, be
at a dosage of less than about 20 Mrad, e.g., from about 0.1 to 15
Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.
[0259] The processes described herein can produce various
by-product streams useful for generating steam and electricity to
be used in other parts of the plant (co-generation) or sold on the
open market. For example, steam generated from burning by-product
streams can be used in a distillation process. As another example,
electricity generated from burning by-product streams can be used
to power electron beam generators used in pretreatment.
[0260] The by-products used to generate steam and electricity are
derived from a number of sources throughout the process. For
example, anaerobic digestion of wastewater can produce a biogas
high in methane and a small amount of waste biomass (sludge). As
another example, post-saccharification and/or post-distillate
solids (e.g., unconverted lignin, cellulose, and hemicellulose
remaining from the pretreatment and primary processes) can be used,
e.g., burned, as a fuel.
[0261] Other intermediates and products, including food and
pharmaceutical products, are described in U.S. Pat. App. Pub.
2010/0124583 A1, published May 20, 2010, to Medoff, the full
disclosure of which is hereby incorporated by reference herein.
Lignin Derived Products
[0262] The spent biomass (e.g., spent lignocellulosic material)
from lignocellulosic processing by the methods described are
expected to have a high lignin content and in addition to being
useful for producing energy through combustion in a Co-Generation
plant, may have uses as other valuable products. For example, the
lignin can be used as captured as a plastic, or it can be
synthetically upgraded to other plastics. In some instances, it can
also be converted to lignosulfonates, which can be utilized as
binders, dispersants, emulsifiers or as sequestrants.
[0263] When used as a binder, the lignin or a lignosulfonate can,
e.g., be utilized in coal briquettes, in ceramics, for binding
carbon black, for binding fertilizers and herbicides, as a dust
suppressant, in the making of plywood and particle board, for
binding animal feeds, as a binder for fiberglass, as a binder in
linoleum paste and as a soil stabilizer.
[0264] As a dispersant, the lignin or lignosulfonates can be used,
e.g., concrete mixes, clay and ceramics, dyes and pigments, leather
tanning and in gypsum board.
[0265] As an emulsifier, the lignin or lignosulfonates can be used,
e.g., in asphalt, pigments and dyes, pesticides and wax
emulsions.
[0266] As a sequestrant, the lignin or lignosulfonates can be used,
e.g., in micro-nutrient systems, cleaning compounds and water
treatment systems, e.g., for boiler and cooling systems.
[0267] For energy production lignin generally has a higher energy
content than holocellulose (cellulose and hemicellulose) since it
contains more carbon than holocellulose. For example, dry lignin
can have an energy content of between about 11,000 and 12,500 BTU
per pound, compared to 7,000 an 8,000 BTU per pound of
holocellulose. As such, lignin can be densified and converted into
briquettes and pellets for burning. For example, the lignin can be
converted into pellets by any method described herein. For a slower
burning pellet or briquette, the lignin can be crosslinked, such as
applying a radiation dose of between about 0.5 Mrad and 5 Mrad.
Crosslinking can make a slower burning form factor. The form
factor, such as a pellet or briquette, can be converted to a
"synthetic coal" or charcoal by pyrolyzing in the absence of air,
e.g., at between 400 and 950.degree. C. Prior to pyrolyzing, it can
be desirable to crosslink the lignin to maintain structural
integrity.
[0268] Co-generation using spent biomass is described in
International App. No. PCT/US2014/021634 filed Mar. 7, 2014, the
entire disclosure therein is herein incorporated by reference.
[0269] Lignin derived products can also be combined with PLA and
PLA derived products. (e.g., PLA that has been produced as
described herein). For example, lignin and lignin derived products
can be blended, grafted to or otherwise combined and/or mixed with
PLA. The lignin can, for example, be useful for strengthening,
plasticizing or otherwise modifying the PLA.
Saccharification
[0270] The treated biomass materials can be saccharified, generally
by combining the material and a cellulase enzyme in a fluid medium,
e.g., an aqueous solution. In some cases, the material is boiled,
steeped, or cooked in hot water prior to saccharification, as
described in U.S. Pat. App. Pub. 2012/0100577 A1 by Medoff and
Masterman, published on Apr. 26, 2012, the entire contents of which
are incorporated herein.
[0271] The saccharification may be done by inoculating a raw sugar
mixture produced by saccharifying a reduced recalcitrance
lignocellulosic material to produce a hydroxy-carboxylic acid. The
hydroxy-carboxylic acid can be selected from the group glycolic
acid, D-lactic acid, L-lactic acid, D-malic acid, L-malic, citric
acid and D-tartaric acid, L-tartaric acid, and meso-tartaric acid.
The raw sugar mixture can be the reduced recalcitrance
lignocellulosic material which was processed by irradiating the
lignocellulosic material with an electron beam.
[0272] The saccharification process can be partially or completely
performed in a tank (e.g., a tank having a volume of at least 4000,
40,000, or 500,000 L) in a manufacturing plant, and/or can be
partially or completely performed in transit, e.g., in a rail car,
tanker truck, or in a supertanker or the hold of a ship. The time
required for complete saccharification will depend on the process
conditions and the carbohydrate-containing material and enzyme
used. If saccharification is performed in a manufacturing plant
under controlled conditions, the cellulose may be substantially
entirely converted to sugar, e.g., glucose in about 12-96 hours. If
saccharification is performed partially or completely in transit,
saccharification may take longer.
[0273] It is generally preferred that the tank contents be mixed
during saccharification, e.g., using jet mixing as described in
International App. No. PCT/US2010/035331, filed May 18, 2010, which
was published in English as WO 2010/135380 and designated the
United States, the full disclosure of which is incorporated by
reference herein.
[0274] The addition of surfactants can enhance the rate of
saccharification. Examples of surfactants include non-ionic
surfactants, such as a Tween.RTM. 20 or Tween.RTM. 80 polyethylene
glycol surfactants, ionic surfactants, or amphoteric
surfactants.
[0275] It is generally preferred that the concentration of the
sugar solution resulting from saccharification be relatively high,
e.g., greater than 40%, or greater than 50, 60, 70, 80, 90 or even
greater than 95% by weight. Water may be removed, e.g., by
evaporation, to increase the concentration of the sugar solution.
This reduces the volume to be shipped, and also inhibits microbial
growth in the solution.
[0276] Alternatively, sugar solutions of lower concentrations may
be used, in which case it may be desirable to add an antimicrobial
additive, e.g., a broad spectrum antibiotic, in a low
concentration, e.g., 50 to 150 ppm. Other suitable antibiotics
include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin,
gentamicin, hygromycin B, kanamycin, neomycin, penicillin,
puromycin, streptomycin. Antibiotics will inhibit growth of
microorganisms during transport and storage, and can be used at
appropriate concentrations, e.g., between 15 and 1000 ppm by
weight, e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If
desired, an antibiotic can be included even if the sugar
concentration is relatively high. Alternatively, other additives
with anti-microbial of preservative properties may be used.
Preferably the antimicrobial additive(s) are food-grade.
[0277] A relatively high concentration solution can be obtained by
limiting the amount of water added to the carbohydrate-containing
material with the enzyme. The concentration can be controlled,
e.g., by controlling how much saccharification takes place. For
example, concentration can be increased by adding more
carbohydrate-containing material to the solution. In order to keep
the sugar that is being produced in solution, a surfactant can be
added, e.g., one of those discussed above. Solubility can also be
increased by increasing the temperature of the solution. For
example, the solution can be maintained at a temperature of
40-50.degree. C., 60-80.degree. C., or even higher.
Saccharifying Agents
[0278] Suitable cellulolytic enzymes include cellulases from
species in the genera Bacillus, Coprinus, Myceliophthora,
Cephalosporium, Scytalidium, Penicillium, Aspergillus, Pseudomonas,
Humicola, Fusarium, Thielavia, Acremonium, Chrysosporium and
Trichoderma, especially those produced by a strain selected from
the species Aspergillus (see, e.g., EP Pub. No. 0 458 162),
Humicola insolens (reclassified as Scytalidium thermophilum, see,
e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusarium
oxysporum, Myceliophthora thermophila, Meripilus giganteus,
Thielavia terrestris, Acremonium sp. (including, but not limited
to, A. persicinum, A. acremonium, A. brachypenium, A.
dichromosporum, A. obclavatum, A. pinkertoniae, A. roseogriseum, A.
incoloratum, and A. furatum). Preferred strains include Humicola
insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora
thermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp.
CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS
169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. CBS
535.71, Acremonium brachypenium CBS 866.73, Acremonium
dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74,
Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS
134.56, Acremonium incoloratum CBS 146.62, and Acremonium furatum
CBS 299.70H. Cellulolytic enzymes may also be obtained from
Chrysosporium, preferably a strain of Chrysosporium lucknowense.
Additional strains that can be used include, but are not limited
to, Trichoderma (particularly T. viride, T. reesei, and T.
koningii), alkalophilic Bacillus (see, for example, U.S. Pat. No.
3,844,890 and EP Pub. No. 0 458 162), and Streptomyces (see, e.g.,
EP Pub. No. 0 458 162).
[0279] In addition to or in combination to enzymes, acids, bases
and other chemicals (e.g., oxidants) can be utilized to saccharify
lignocellulosic and cellulosic materials. These can be used in any
combination or sequence (e.g., before, after and/or during addition
of an enzyme). For example, strong mineral acids can be utilized
(e.g. HCl, H.sub.2SO.sub.4, H.sub.3PO.sub.4) and strong bases
(e.g., NaOH, KOH).
Sugars
[0280] In the processes described herein, for example, after
saccharification, sugars (e.g., glucose and xylose) can be
isolated. For example, sugars can be isolated by precipitation,
crystallization, chromatography (e.g., simulated moving bed
chromatography, high pressure chromatography), centrifugation,
extraction, any other isolation method known in the art, and
combinations thereof.
Hydrogenation and Other Chemical Transformations
[0281] The processes described herein can include hydrogenation.
For example, glucose and xylose can be hydrogenated to sorbitol and
xylitol respectively. Esters, for example, produced as described
herein, can also be hydrogenated. Hydrogenation can be accomplished
by use of a catalyst (e.g., Pt/gamma-Al.sub.2O.sub.3, Ru/C, Raney
Nickel, copper chromite or other catalysts know in the art) in
combination with H.sub.2 under high pressure (e.g., 10 to 12000
psi). Other types of chemical transformation of the products from
the processes described herein can be used, for example, production
of organic sugar derived products such (e.g., furfural and
furfural-derived products). Chemical transformations of sugar
derived products are described in International App. No.
PCT/US201/049562, filed Jul. 3, 2013, the disclosure of which is
incorporated herein by reference in its entirety.
Fermentation
[0282] Yeast and Zymomonas bacteria, for example, can be used for
fermentation or conversion of sugar(s) to alcohol(s). Other
microorganisms are discussed below. The optimum pH for
fermentations is about pH 4 to 7. For example, the optimum pH for
yeast is from about pH 4 to 5, while the optimum pH for Zymomonas
is from about pH 5 to 6. Typical fermentation times are about 24 to
168 hours (e.g., 24 to 96 hrs.) with temperatures in the range of
20.degree. C. to 40.degree. C. (e.g., 26.degree. C. to 40.degree.
C.), however thermophilic microorganisms prefer higher
temperatures.
[0283] In some embodiments, e.g., when anaerobic organisms are
used, at least a portion of the fermentation is conducted in the
absence of oxygen, e.g., under a blanket of an inert gas such as
N.sub.2, Ar, He, CO.sub.2 or mixtures thereof. Additionally, the
mixture may have a constant purge of an inert gas flowing through
the tank during part of or all of the fermentation. In some cases,
anaerobic condition, can be achieved or maintained by carbon
dioxide production during the fermentation and no additional inert
gas is needed.
[0284] In some embodiments, all or a portion of the fermentation
process can be interrupted before the low molecular weight sugar is
completely converted to a product (e.g., ethanol). The intermediate
fermentation products include sugar and carbohydrates in high
concentrations. The sugars and carbohydrates can be isolated via
any means known in the art. These intermediate fermentation
products can be used in preparation of food for human or animal
consumption. Additionally or alternatively, the intermediate
fermentation products can be ground to a fine particle size in a
stainless-steel laboratory mill to produce a flour-like substance.
Jet mixing may be used during fermentation, and in some cases
saccharification and fermentation are performed in the same
tank.
[0285] Nutrients for the microorganisms may be added during
saccharification and/or fermentation, for example, the food-based
nutrient packages described in U.S. Pat. App. Pub. 2012/0052536,
filed Jul. 15, 2011, the complete disclosure of which is
incorporated herein by reference.
[0286] "Fermentation" includes the methods and products that are
disclosed in International App. No. PCT/US2012/071093 filed Dec.
20, 2012 and International App. No. PCT/US2012/071097 filed Dec.
12, 2012, the contents of both of which are incorporated by
reference herein in their entirety.
[0287] Mobile fermenters can be utilized, as described in
International App. No. PCT/US2007/074028 (which was filed Jul. 20,
2007, was published in English as WO 2008/011598 and designated the
United States) and has a US issued U.S. Pat. No. 8,318,453, the
contents of which are incorporated herein in its entirety.
Similarly, the saccharification equipment can be mobile. Further,
saccharification and/or fermentation may be performed in part or
entirely during transit.
Fermentation Agents
[0288] The microorganism(s) used in fermentation can be
naturally-occurring microorganisms and/or engineered
microorganisms. For example, the microorganism can be a bacterium
(including, but not limited to, e.g., a cellulolytic bacterium), a
fungus, (including, but not limited to, e.g., a yeast), a plant, a
protist, e.g., a protozoa or a fungus-like protest (including, but
not limited to, e.g., a slime mold), or an alga. When the organisms
are compatible, mixtures of organisms can be utilized.
[0289] Suitable fermenting microorganisms have the ability to
convert carbohydrates, such as glucose, fructose, xylose,
arabinose, mannose, galactose, oligosaccharides or polysaccharides
into fermentation products. Fermenting microorganisms include
strains of the genus Saccharomyces spp. (including, but not limited
to, S. cerevisiae (baker's yeast), S. distaticus, S. uvarum), the
genus Kluyveromyces, (including, but not limited to, K. marxianus,
K. fragilis), the genus Candida (including, but not limited to, C.
pseudotropicalis, and C. brassicae), Pichia stipitis (a relative of
Candida shehatae), the genus Clavispora (including, but not limited
to, C. lusitaniae and C. opuntiae), the genus Pachysolen
(including, but not limited to, P. tannophilus), the genus
Bretannomyces (including, but not limited to, e.g., B. clausenii
(Philippidis, G. P., 1996, Cellulose bioconversion technology, in
Handbook on Bioethanol: Production and Utilization, Wyman, C. E.,
ed., Taylor & Francis, Washington, DC, 179-212)). Other
suitable microorganisms include, for example, Zymomonas mobilis,
Clostridium spp. (including, but not limited to, C. thermocellum
(Philippidis, 1996, supra), C. saccharobutylacetonicum, C.
tyrobutyricum C. saccharobutylicum, C. Puniceum, C. beijemckii, and
C. acetobutylicum), Moniliella spp. (including but not limited to
M. pollinis, M. tomentosa, M. madida, M. nigrescens, M.
oedocephali, M. megachiliensis), Yarrowia lipolytica, Aureobasidium
sp., Trichosporonoides sp., Trigonopsis variabilis, Trichosporon
sp., Moniliellaacetoabutans sp., Typhula variabilis, Candida
magnoliae, Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast
species of genera Zygosaccharomyces, Debaryomyces, Hansenula and
Pichia, and fungi of the dematioid genus Torula (e.g., T.
corallina).
[0290] Many such microbial strains are publicly available, either
commercially or through depositories such as the ATCC (American
Type Culture Collection, Manassas, Va., USA), the NRRL
(Agricultural Research Service Culture Collection, Peoria, Ill.,
USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen and
Zellkulturen GmbH, Braunschweig, Germany), to name a few.
[0291] Commercially available yeasts include, for example, Red
Star.RTM./Lesaffre Ethanol Red (available from Red Star/Lesaffre,
USA), FALI.RTM. (available from Fleischmann's Yeast, a division of
Burns Philip Food Inc., USA), SUPERSTART.RTM. (available from
Alltech, now Lallemand), GERT STRAND.RTM. (available from Gert
Strand AB, Sweden) and FERMOL.RTM. (available from DSM
Specialties).
Distillation
[0292] After fermentation, the resulting fluids can be distilled
using, for example, a "beer column" to separate ethanol and other
alcohols from the majority of water and residual solids. The vapor
exiting the beer column can be, e.g., 35% by weight ethanol and can
be fed to a rectification column. A mixture of nearly azeotropic
(92.5%) ethanol and water from the rectification column can be
purified to pure (99.5%) ethanol using vapor-phase molecular
sieves. The beer column bottoms can be sent to the first effect of
a three-effect evaporator. The rectification column reflux
condenser can provide heat for this first effect. After the first
effect, solids can be separated using a centrifuge and dried in a
rotary dryer. A portion (25%) of the centrifuge effluent can be
recycled to fermentation and the rest sent to the second and third
evaporator effects. Most of the evaporator condensate can be
returned to the process as fairly clean condensate with a small
portion split off to waste water treatment to prevent build-up of
low-boiling compounds.
Hydrocarbon-Containing Materials
[0293] In other embodiments utilizing the methods and systems
described herein, hydrocarbon-containing materials can be
processed. Any process described herein can be used to treat any
hydrocarbon-containing material herein described.
"Hydrocarbon-containing materials," as used herein, is meant to
include oil sands, oil shale, tar sands, coal dust, coal slurry,
bitumen, various types of coal, and other naturally-occurring and
synthetic materials that include both hydrocarbon components and
solid matter. The solid matter can include rock, sand, clay, stone,
silt, drilling slurry, or other solid organic and/or inorganic
matter. The term can also include waste products such as drilling
waste and by-products, refining waste and by-products, or other
waste products containing hydrocarbon components, such as asphalt
shingling and covering, asphalt pavement, etc.
Conveying Systems
[0294] Various conveying systems can be used to convey the
feedstock materials, for example, to a vault and under an electron
beam in a vault. Exemplary conveyors are belt conveyors, pneumatic
conveyors, screw conveyors, carts, trains, trains or carts on
rails, elevators, front loaders, backhoes, cranes, various scrapers
and shovels, trucks, and throwing devices can be used. For example,
vibratory conveyors can be used in various processes described
herein, for example, as disclosed in International App. No.
PCT/US2013/064332 filed Oct. 10, 2013, the entire disclosure of
which is herein incorporated by reference.
Other Embodiments
[0295] Any material, processes or processed materials described
herein can be used to make products and/or intermediates such as
composites, fillers, binders, plastic additives, adsorbents and
controlled release agents. The methods can include densification,
for example, by applying pressure and heat to the materials. For
example, composites can be made by combining fibrous materials with
a resin or polymer (e.g., PLA). For example, radiation
cross-linkable resin (e.g., a thermoplastic resin, PLA, and/or PLA
derivatives) can be combined with a fibrous material to provide a
fibrous material/cross-linkable resin combination. Such materials
can be, for example, useful as building materials, protective
sheets, containers and other structural materials (e.g., molded
and/or extruded products). Absorbents can be, for example, in the
form of pellets, chips, fibers and/or sheets. Adsorbents can be
used, for example, as pet bedding, packaging material or in
pollution control systems. Controlled release matrices can also be
the form of, for example, pellets, chips, fibers and or sheets. The
controlled release matrices can, for example, be used to release
drugs, biocides, fragrances. For example, composites, absorbents
and control release agents and their uses are described in
International Application No. PCT/US2006/010648, filed Mar. 23,
2006, and U.S. Pat. No. 8,074,910 filed Nov. 22, 2011, the entire
disclosures of which are herein incorporated by reference.
[0296] In some instances the biomass material is treated at a first
level to reduce recalcitrance, e.g., utilizing accelerated
electrons, to selectively release one or more sugars (e.g.,
xylose). The biomass can then be treated to a second level to
release one or more other sugars (e.g., glucose). Optionally the
biomass can be dried between treatments. The treatments can include
applying chemical and biochemical treatments to release the sugars.
For example, a biomass material can be treated to a level of less
than about 20 Mrad (e.g., less than about 15 Mrad, less than about
10 Mrad, less than about 5 Mrad, less than about 2 Mrad) and then
treated with a solution of sulfuric acid, containing less than 10%
sulfuric acid (e.g., less than about 9%, less than about 8%, less
than about 7%, less than about 6%, less than about 5%, less than
about 4%, less than about 3%, less than about 2%, less than about
1%, less than about 0.75%, less than about 0.50%, less than about
0.25%) to release xylose. Xylose, for example, that is released
into solution, can be separated from solids and optionally the
solids washed with a solvent/solution (e.g., with water and/or
acidified water). Optionally, the Solids can be dried, for example,
in air and/or under vacuum optionally with heating (e.g., below
about 150.degree. C., below about 120.degree. C.) to a water
content below about 25 wt. % (below about 20 wt. %, below about 15
wt. %, below about 10 wt. %, below about 5 wt. %). The solids can
then be treated with a level of less than about 30 Mrad (e.g., less
than about 25 Mrad, less than about 20 Mrad, less than about 15
Mrad, less than about 10 Mrad, less than about 5 Mrad, less than
about 1 Mrad or even not at all) and then treated with an enzyme
(e.g., a cellulase) to release glucose. The glucose (e.g., glucose
in solution) can be separated from the remaining solids. The solids
can then be further processed, for example, utilized to make energy
or other products (e.g., lignin derived products).
EXAMPLES
L-Lactic Acid Production from Saccharified Corncob in Lactobacillus
Species
Material and Methods
Lactic Acid Producing Strains Tested:
[0297] The Lactic acid producing stains that were tested are listed
in Table 2
TABLE-US-00003 TABLE 2 Lactic acid producing strains tested NRRL
B-441 Lactobacillus casei NRRL B-445 Lactobacillus rhamnosus NRRL
B-763 Lactobacillus delbrueckii subspecies delbrueckii ATCC 8014
Lactobacillus plantarum ATCC 9649 Lactobacillus delbrueckii
subspecies delbrueckii B-4525 Lactobacillus delbrueckii subspecies
lactis B-4390 Lactobacillus coryniformis subspecies torquens B-227
Lactobacillus pentosus B-4527 Lactobacillus brevis ATCC 25745
Pediococcus pentosaceus NRRL 395 Rhizopus oryzae CBS 112.07
Rhizopus oryzae CBS 127.08 Rhizopus oryzae CBS 396.95 Rhizopus
oryzae
Seed Culture
[0298] Cells from a frozen (-80.degree. C.) cell bank were
cultivated in propagation medium (BD DIFCO.TM. Lactobacilli MRS
Broth) at 37.degree. C., with 150 rpm stirring for 20 hours. This
seed culture was transferred to a 1.2 L (or optionally a 20 L)
bioreactors charged with media as describe below.
Main Culture Media
[0299] All media included saccharified corncob that had been hammer
milled and irradiated with about 35 Mrad of electron beam
irradiation. For example, saccharified corn cob can be prepared as
described in International App. No. PCT/US2014/021796 filed Mar. 7,
2014, the entire disclosure of which is herein incorporated by
reference.
[0300] Experiments with various additional media components were
also conducted using Lactobacillus casei NRRL B-44 as the lactic
acid producing organism. A 1.2 L bioreactor with 0.7 L of culture
volume was used. A 1% of 20-hour-cultured seed of Lactobacillus
casei NRRL B-441 was inoculated. No aeration was utilized. The
temperature was maintained at about 37.degree. C. Antifoam 204 was
also added (0.1%, 1 ml/L) at the beginning of the fermentation.
[0301] The experiments are summarized in Table 3. The media
components; initial glucose concentration, nitrogen sources, yeast
extract concentration, calcium carbonate, metals and inoculum size,
were tested for lactic acid yield or lactic acid production rate.
In addition to media components, the physical conditions;
temperature, agitation, autoclave time and heating (no-autoclave)
were tested for lactic acid yield. For these media components and
physical reaction conditions the ranges tested, ranges for
producing some lactic acid and the ranges are indicated in Table
3.
TABLE-US-00004 TABLE 3 L-Lactic acid production in bioreactor with
B-441 Media Test Component Parameter Range-Tested Range.sup.a
Range-Optional.sup.b Initial glucose Lactic acid 33-85 g/L 33-75
g/L 33-52 g/L concentration concentration Nitrogen Lactic acid
Yeast extract, Yeast extract, Yeast extract Sources Tested
concentration Malt extract, Tryptone, Corn steep, Peptone Tryptone,
Peptone Yeast Extract .sup.c Lactic acid 0-10 g/L 2.5-10 g/L 2.5
g/L concentration Calcium Lactic acid 0-7 wt. %/vol. % 3-7% wt.
%/vol. % 5 wt. %/vol. % carbonate concentration Metal Solutions
Lactic acid With or without With or Without metals concentration
metals without metals Minor Lactic acid With or without With or
Without minor components: concentration minor without minor
components sodium acetate components components Polysorbate .TM.
80.sup.d, dipotassium hydrogen phosphate, triammonium citrate
Inoculum Size Lactic acid 0.1-5 vol. % 1-5 vol. % 1 vol. %
production rate Physical Test Condition Parameter Range-Tested
Range- Range Temperature Lactic acid 27-47.degree. C. 27-42.degree.
C. 33-37.degree. C. concentration Agitation (in Lactic acid 50-400
rpm 50-400 rpm 100-300 rpm 1.2L reactor) concentration Autoclave
Time Lactic acid 25 min-145 min 25 min-145 min 25 min concentration
Heating (no Lactic acid 50-70.degree. C. 50-70.degree. C.
50-70.degree. C. autoclave) concentration .sup.aRanges produced a
yield of at least 80% based on added sugars. .sup.bOptional ranges
produced close to 100% lactic acid (e.g., between about 90 and
100%, between about 95 and 100%) .sup.c Fluka brand yeast extract
was used. .sup.dPolysorbate .TM.80 is a nonionic surfactant from
ICI Americas, Inc.
Results with Optional Media and Optional Physical Conditions
[0302] A 1.2 L bioreactor charged with 0.7 L of media (Saccharified
corncob, 2.5 g/L yeast extract). The media and bioreactor vessel
were autoclaved for 25 min and no additional heating was used for
sterilization. In addition a 20 L bioreactor was charged with 10 L
of media. For sterilization the media was stirred at 200 rpm while
heating at 80.degree. C. for 10 min. When the media was cool (about
37.degree. C.) the bioreactors were inoculated with 1 vol. % of
20-hour-culture. The fermentations were conducted under the
physical conditions (37.degree. C., 200 rpm stirring). No aeration
was utilized. The pH remained between 5 and 6 using 5% (wt. %/vol.
%) throughout the fermentation. The temperature was maintained at
about 37.degree. C. Antifoam 204 was also added (0.1vol. %) at the
beginning of the fermentation. Several Lactobacillus casei strains
were tested (NRRL B-441, NRRL B-445, NRRL B-763 and ATCC 8014).
[0303] A plot of the sugar consumption and lactic acid production
for the NRRL B-441 strain is shown in the 1.2 L bioreactor is shown
in FIG. 7. After two days all of the glucose was consumed, while
xylose was not consumed. Fructose and cellobiose were also
consumed. Lactic acid was produced at a concentration of about 42
g/L. The consumed glucose, fructose and cellobiose (total 42 g/L)
were about to same as produced lactic acid.
[0304] Similar data from results of the fermentation using the NRRL
B-441 strain in the 20 L bioreactor are shown in FIG. 8. Glucose
was completely consumed while xylose was not significantly
consumed. Lactic acid was produced at a final concentration of
about 47-48 g/L.
[0305] Enantiomer analysis is summarized for all strains tested in
Table 4. Lactobacillus casei (NRRL-B-441) and L. rhamnosus (B-445)
produced more than 96% L-lactic acid. L. delbrueckii sub.
Delbrueckii (B-763) showed over 99% of the D-Lactic acid. The L.
plantarum (ATCC 8014) showed an approximate equal mixture of each
enantiomer.
TABLE-US-00005 TABLE 4 Ratio of L and D-Lactic Acid for Various
Fermenting Organisms Strain L-Lactic Acid D-Lactic Acid L. casei
(B-441) 96.1 3.9 L. rhamnosus (B-445) 98.3 1.7 L. delbrueckii sub.
0.6 99.4 Delbrueckii (B-763) L. plantarum (ATCC 8014) 52.8 47.2
Polymerization of Lactic Acid
[0306] A 250 ml three-necked flask was equipped with a mechanical
stirrer and a condenser that was connected with a vacuum system
through a cold trap. 100 grams of 90 wt. % aqueous L-lactic acid
was dehydrated at 150.degree. C., first at atmospheric pressure for
2 hours, then at a reduced pressure of 90 mmHg for 2 hours, and
finally under a pressure of 20 mmHg for another 4 hours. A clear
viscous liquid of oligo(L-lactic acid) was formed
quantitatively.
[0307] 400 mg (0.4 wt. %) of both tin(II) chloride dihydrate and
para-toluene sulfonic acid was acid was added to the mixture and
further heated to 180.degree. C. for 5 hours at 8 mmHg With the
reaction proceeding, the system became more viscous gradually. The
reaction mixture was cooled down and then further heated at
150.degree. C. in a vacuum oven another 19 hours.
[0308] Samples were taken from the reaction mixture after 2 hours
(A), 5 hours (B) and 24 hours (C) and the molecular weight was
calculated using GPC using polystyrene standards in THF. FIG. 9 is
a plot of GPC data for samples A, B and C.
TABLE-US-00006 Reaction time Molecular Retention Sample (hours)
Weight Time A 2 8000 18.3 B 5 12000 19.3 C 24 35000 20.3
[0309] Other than in the examples herein, or unless otherwise
expressly specified, all of the numerical ranges, amounts, values
and percentages, such as those for amounts of materials, elemental
contents, times and temperatures of reaction, ratios of amounts,
and others, in the following portion of the specification and
attached claims may be read as if prefaced by the word "about" even
though the term "about" may not expressly appear with the value,
amount, or range. Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should at least be construed in
light of the number of reported significant digits and by applying
ordinary rounding techniques.
[0310] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains error necessarily resulting from the standard
deviation found in its underlying respective testing measurements.
Furthermore, when numerical ranges are set forth herein, these
ranges are inclusive of the recited range end points (i.e., end
points may be used). When percentages by weight are used herein,
the numerical values reported are relative to the total weight.
[0311] Also, it should be understood that any numerical range
recited herein is intended to include all sub-ranges subsumed
therein. For example, a range of "1 to 10" is intended to include
all sub-ranges between (and including) the recited minimum value of
1 and the recited maximum value of 10, that is, having a minimum
value equal to or greater than 1 and a maximum value of equal to or
less than 10. The terms "one," "a," or "an" as used herein are
intended to include "at least one" or "one or more," unless
otherwise indicated.
[0312] Any patent, publication, or other disclosure material, in
whole or in part, that is said to be incorporated by reference
herein is incorporated herein only to the extent that the
incorporated material does not conflict with existing definitions,
statements, or other disclosure material set forth in this
disclosure. As such, and to the extent necessary, the disclosure as
explicitly set forth herein supersedes any conflicting material
incorporated herein by reference. Any material, or portion thereof,
that is said to be incorporated by reference herein, but which
conflicts with existing definitions, statements, or other
disclosure material set forth herein will only be incorporated to
the extent that no conflict arises between that incorporated
material and the existing disclosure material.
[0313] While this invention has been particularly shown and
described with references to most preferred embodiments thereof, it
will be understood by those skilled in the art that various changes
in form and details may be made therein without departing from the
scope of the invention encompassed by the appended claims.
* * * * *