U.S. patent application number 13/768702 was filed with the patent office on 2013-08-15 for bioadhesives and processes for making same.
This patent application is currently assigned to GS CLEANTECH CORPORATION. The applicant listed for this patent is GS Cleantech Corporation. Invention is credited to Forrest L. Dahmes, Kevin E. Kreisler, Michael J. Riebel, David J. Winsness.
Application Number | 20130206336 13/768702 |
Document ID | / |
Family ID | 47755060 |
Filed Date | 2013-08-15 |
United States Patent
Application |
20130206336 |
Kind Code |
A1 |
Riebel; Michael J. ; et
al. |
August 15, 2013 |
BIOADHESIVES AND PROCESSES FOR MAKING SAME
Abstract
A dried distiller soluble based bioadhesive composition and
method for producing the dried distiller soluble based bioadhesives
are disclosed, as well as derivatives thereof. The produced dried
distillers solubles derives from co-products of corn fermentation
facilities, and is advantageously comprised in part of
water-soluble proteins. The method for producing the dried
distillers solubles generally involves separation and/or
introduction of targeted constituents and/or physiochemical
treatment to facilitate use as an adhesive. Use of the method and
bioadhesive compositions disclosed herein will improve the
economics of fermentation by increasing co-product value, reducing
plant-wide energy utilization, decreasing waste and emissions, and
increasing overall product yield from each bushel of corn
consumed.
Inventors: |
Riebel; Michael J.;
(Mankato, MN) ; Winsness; David J.; (Alpharetta,
GA) ; Dahmes; Forrest L.; (Hawick, MN) ;
Kreisler; Kevin E.; (Mount Arlington, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
GS Cleantech Corporation; |
|
|
US |
|
|
Assignee: |
GS CLEANTECH CORPORATION
New York
NY
|
Family ID: |
47755060 |
Appl. No.: |
13/768702 |
Filed: |
February 15, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61599215 |
Feb 15, 2012 |
|
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61614862 |
Mar 23, 2012 |
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Current U.S.
Class: |
156/336 ;
106/156.2; 106/156.51; 106/157.8 |
Current CPC
Class: |
C09J 189/04 20130101;
C07K 14/415 20130101; Y02E 50/17 20130101; C08H 99/00 20130101;
Y02E 50/10 20130101; B01D 1/18 20130101; C12F 3/10 20130101; C08H
1/00 20130101; C08J 11/04 20130101; B01J 2/06 20130101; C08B 37/00
20130101; B01J 2/04 20130101; C08L 97/02 20130101; C08L 101/16
20130101 |
Class at
Publication: |
156/336 ;
106/156.51; 106/156.2; 106/157.8 |
International
Class: |
C09J 189/04 20060101
C09J189/04 |
Claims
1. A bioadhesive composition comprising dried distillers
solubles.
2. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a tackifier selected from the
group consisting of natural rosins, modified rosins, copolymers of
natural terpenes, polyterpene resins, aliphatic hydrocarbon resins,
and combinations thereof.
3. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a plasticizer selected from the
group consisting of olefin oligomers, phthalates, mineral oils,
vegetal oils, animal oils, and combinations thereof.
4. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a crosslinker.
5. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a wax selected from the group
consisting of petroleum waxes, polyolefin waxes, synthetic waxes,
paraffin, microcrystalline waxes, and combinations thereof.
6. The bioadhesive composition of claim 1, wherein the dried
distillers solubles comprise modified water soluble proteins.
7. The bioadhesive composition of claim 1, further comprising a soy
bean protein isolate.
8. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a filler selected from the group
consisting of sand, talc, clay, silica, mica, magnesium oxide,
mica, silicon dioxide, kaolin, iron oxide, and combinations
thereof.
9. The bioadhesive composition of claim 1, further comprising an
additive, wherein the additive is a fiber selected from cellulose
fibers and synthetic fibers.
10. A method of making a bioadhesive composition comprising:
evaporating at least a portion of water from thin stillage obtained
from a corn-to-ethanol fermentation process to form condensed
distillers solubles; drying the condensed distillers solubles to
form dried distillers solubles; and forming a bioadhesive
composition with the dried distillers solubles.
11. The method of claim 10, further comprising wet compounding the
dried distillers solubles with an additive.
12. The method of claim 10, further comprising dry compounding the
dried distillers solubles with an additive.
13. The method of claim 11, wherein the additive comprises a
plasticizer, a crosslinker, a wax, a filler material, a soy protein
isolate, an antioxidant, a UV stabilizer, a colorant, a flow aid, a
biocide, a lubricant, an oil, a coupling agent, a fiber, a
tackifier, a metal oxide, a surfactant, a catalyst, a solvent, or a
hydrolyzing agent, or mixtures thereof.
14. The method of claim 11, wherein the plasticizer is selected
from the group consisting of olefin oligomers, phthalates, mineral
oils, vegetal oils, animal oils, and combinations thereof.
15. The method of claim 11, wherein the tackifier is selected from
the group consisting of natural rosins, modified rosins, copolymers
of natural terpenes, polyterpene resins, aliphatic hydrocarbon
resins, and combinations thereof.
16. The method of claim 11, wherein the wax is selected from the
group consisting of petroleum waxes, polyolefin waxes, synthetic
waxes, paraffin, microcrystalline waxes, and combinations
thereof.
17. The method of claim 11, wherein the filler is selected from the
group consisting of sand, talc, clay, silica, mica, magnesium
oxide, mica, silicon dioxide, kaolin, iron oxide, and combinations
thereof.
18. The method of claim 12, wherein the additive comprises a
plasticizer, a crosslinker, a wax, a filler material, a soy protein
isolate, a fiber, a metal oxide or mixtures thereof.
19. The method of claim 12, wherein the plasticizer is selected
from the group consisting of olefin oligomers, phthalates, mineral
oils, vegetal oils, animal oils, and combinations thereof.
20. The method of claim 12, wherein the tackifier is selected from
the group consisting of natural rosins, modified rosins, copolymers
of natural terpenes, polyterpene resins, aliphatic hydrocarbon
resins, and combinations thereof.
21. The method of claim 12, wherein the wax is selected from the
group consisting of petroleum waxes, polyolefin waxes, synthetic
waxes, paraffin, microcrystalline waxes, and combinations
thereof.
22. The method of claim 12, wherein the filler is selected from the
group consisting of sand, talc, clay, silica, mica, magnesium
oxide, mica, silicon dioxide, kaolin, iron oxide, and combinations
thereof.
23. The method of claim 10, further comprising chemically modifying
at least one of a whole stillage, thin stillage, the condensed
distillers solubles and dried distillers solubles.
24. The method of claim 10, further comprising removing a selected
amount of oil from the condensed distillers solubles such that the
dried distillers solubles contains a desired amount of oil
therein.
25. The method of claim 10, further comprising treating the thin
stillage or the condensed distillers solubles with an acid or
base.
26. The method of claim 10, wherein drying comprises convection at
an elevated temperature.
27. The method of claim 10, wherein drying is a drying gas stream
at a temperature of about 600.degree. F. to about 1800.degree.
F.
28. The method of claim 10, wherein evaporating the condensed
distillers solubles comprises reducing the moisture content to less
than about 50% by weight.
29. A process for bonding one component to another component, the
process comprising: applying a bioadhesive composition to a surface
of at least one of the components, wherein the bioadhesive
composition comprises dried distillers solubles; and contacting the
one component with the other component, wherein the bioadhesive
composition is therebetween.
30. The process of claim 29, wherein the dried distillers solubles
is a compactable powder.
31. The process of claim 29 wherein the composition further
comprises a tackifier, a plasticizer, a wax, an antioxidant, a UV
stabilizer, a colorant, a filler, a flow aid, a biocide, a
lubricant, an oil, a coupling agent, a crosslinking agent, a
surfactant, a catalyst, a solvent, or a hydrolyzing agent.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit of the
U.S. Provisional Patent Application Nos. 61/599,215 filed on Feb.
15, 2012 and 61/614,862 filed Mar. 23, 2012, which are fully
incorporated herein by reference.
BACKGROUND
[0002] The present disclosure generally relates to the renewable
fuel, renewable chemical, polymer, plastic, elastomer, resin and
adhesive production industries; and more specifically, to improving
the production, product mix and economics of fermentation
processes, such as corn to ethanol manufacturing processes and the
like. More particularly, the present disclosure relates to
bioadhesives formed from dried distillers solubles produced in the
corn fermentation process.
[0003] Bioadhesives are natural polymeric materials that act as
adhesives. Exemplary bioadhesives are those derived from soy flour.
Soy flour suitable for use as bioadhesives was, and still is,
generally obtained by removing some or most of the oil from the
soybean, yielding a residual soy meal that was subsequently ground
into extremely fine soy flour. The resulting soy flour was then,
generally, denatured (i.e., the secondary, tertiary and/or
quaternary structures of the proteins were altered to expose
additional polar functional groups capable of bonding) with an
alkaline agent and, to some extent, hydrolyzed (i.e., the covalent
bonds were broken) to yield adhesives for wood bonding under dry
conditions.
[0004] The use of soybeans as a bioadhesive has various
limitations. First and foremost is that making a bioadhesive from
soybeans requires removal of the soybean oil. Excessive soybean oil
creates weaker bonds and creates issues during heat pressing of the
adhesive, wherein a Maillard reaction can take place resulting in
browning or blackening of the material, creating a distinct odor
and weakening the overall adhesive value. Moreover, the removal of
oil from soybeans typically uses a flammable hexane extraction
process.
[0005] Soybeans naturally have a relatively high concentration of
carbohydrates. The high concentration of carbohydrates can create
moisture instability issues. In addition, the high carbohydrate
levels in soy flour require more complex crosslinking techniques
and chemistries to improve the water resistance problem of soybean
bioadhesives. The use of soy protein isolates (SPI) have been used,
wherein a chemical process is applied to the soy flour to remove
starch and/or carbohydrates from the soybean meal. This process
creates additional costs and mostly uses hazardous chemistry and
methods.
[0006] Soybean protein flour also requires a separate hydrolyzation
process to make the proteins have an adhesive nature. In most prior
art, water is added to the soybean flour along with a caustic or
chemical that can raise the pH sufficient to hydrolyze the
proteins. Caustic chemicals such as sodium hydroxide, potassium
hydroxides and other harmful chemicals are often used. Not only
does the hydrolyzation process require additional and potentially
harmful chemical processing steps, it further adds to the cost of
such materials.
[0007] Because of the many limitations with the use of soybeans for
preparing bioadhesives, other materials are now being
investigated.
[0008] The U.S. ethanol industry is generally based on the
fermentation of corn. It has grown significantly over the past 30
years, from an industry-wide output of 175 million gallons per year
in 1980 to about 13.5 billion gallons in 2011. Demand for ethanol
in the United States is expected to continue to increase due to a
number of factors, including policies designed to reduce reliance
on fossil fuels, volatile petroleum prices, heightened
environmental concerns, and energy independence and national
security concerns. Corn ethanol can thus be expected to comprise an
increasingly larger portion of the U.S. liquid fuel supply during
the next several years.
[0009] The production and use of renewable chemicals has also grown
significantly in recent years for many of the same reasons, with an
attendant increase in demand for renewable raw materials. As a
result, there is substantial interest and ongoing research
involving development of commercial processes for the conversion of
corn and its derivatives into various renewable fuels and
chemicals, including substitutes for fossil fuel-derived chemicals
and industrial polymers, such as plastics, elastomers, resins, and
adhesives.
[0010] With its established corn fermentation infrastructure, the
U.S. corn ethanol industry can be expected to be the most practical
pathway to increase the production and use of such renewable fuels
and chemicals on globally-meaningful scales. To participate in that
growth, corn fermentation facilities will need to evolve to achieve
improved production efficiencies.
[0011] Because of its relatively low investment and operational
requirements, dry milling has become the primary method for corn to
ethanol production. In the dry milling process, corn is first
screened and ground to a flour. The resulting flour is combined
with water and the starch within the corn is conventionally
hydrolyzed into sugar by liquefaction and saccharification. The
mixture is then fermented with yeast to convert the sugar into
ethanol and carbon dioxide. About 30% of the mass of each kernel of
corn accepted by corn ethanol producers is converted into ethanol
in this manner. The output of fermentation, a mixture of ethanol,
water, protein, carbohydrates, fat, minerals, solids and other
unfermented components, is then distilled to boil off ethanol for
recovery, purification and sale, leaving the remainder of the
mixture in the bottom of the distillation stage.
[0012] The remainder in the bottom of the distillation stage is
referred to as whole stillage and is typically subjected to a press
or centrifugation process to separate the coarse solids from the
liquid. The liquid fraction is commonly referred to as distillers
solubles or thin stillage. Thin stillage is frequently concentrated
in an evaporator to become condensed distillers solubles, which is
also commonly referred to as thin stillage syrup or thin stillage
concentrate. The coarse solids, or wet cake, collected from the
centrifuge or press are known as wet distillers grains. Drying the
distillers grains produces dried distillers grains. The distillers
grains can be combined with the condensed distillers solubles to
form what is commonly referred to as wet distillers grains with
solubles, which can then be dried to form dried distillers grains
with solubles (also referred to as dried distillers solubles). The
dried distillers grains or dried distillers grains with solubles
typically have a moisture content of less than 20% by weight to
greater than 3% by weight although greater or lesser amounts of
moisture content may be employed as may be desired for different
applications.
[0013] In some instances, the condensed distillers solubles is
subjected to a high temperature drying process to form dried
distillers solubles, which reportedly has been used as a
thermoplastic additive with metal oxide and fiber in the
preparation of extruded articles.
[0014] In other instances, partially concentrated thin stillage or
condensed distillers solubles, prior to being combined with the wet
distillers grains, is subjected to a corn oil extraction process to
remove at least a portion of the oil contained therein. The
extracted crude corn oil can be used as a feedstock for the
production of biodiesel and other products. The remaining condensed
distillers solubles with at least a portion of the oil removed is
then typically combined with the wet distillers grains to form the
wet distillers grains with solubles and further dried as dried
distillers grains with solubles for use as animal feed. Exemplary
corn oil extraction processes are disclosed in U.S. Pat. Nos.
7,601,858, 7,608,729, 8,008,516, and 8,008,517, all of which are
incorporated by reference in their entireties.
[0015] The non-fermentable byproducts of the corn to ethanol
fermentation process are currently being investigated for use as
bioadhesives. For example, U.S. Pat. No. 7,618,660 to Mohanty et
al. discloses the use of urea or caustic treated dried distillers
grains with solubles to form a bioadhesive for paperboard binding.
In Monhanty, distiller dried grains with solubles are treated with
urea and/or a strong base such as sodium hydroxide to hydrolyze
water-insoluble proteins. The resulting solution is then filtered
to at least partially remove inert fiber (cellulose and
hemicellulose) and other insoluble materials prior to final
dewatering, leaving a complex mixture of low molecular weight
compounds with low viscosity. The high solids and residual inert
fiber content of the resulting distiller dried grains with
solubles-derived adhesive reduces the overall percentage of active
protein and thus decreases functionality in most resin and adhesive
applications.
[0016] The usage of currently processed dried distillers grains or
dried distillers grains with solubles is problematic for
bioadhesives. Constituent carbohydrates and insoluble components
within the grains must be processed with hazardous chemicals that
require additional process stages, energy, and expensive equipment
comprised of alloys having high corrosion resistance. Secondary
processing to grind the dried distillers grains or dried distillers
grains with solubles into a fine powder would also be required.
Building and operating such processes at the scale would be very
expensive and would yield an adhesive with functionality diminished
by the presence of high concentrations of carbohydrates and
insoluble materials.
[0017] Accordingly, it would be desirable for a more robust
renewable material for bioadhesives that does not possess these
limitations.
BRIEF SUMMARY
[0018] Disclosed herein are dried distiller soluble based
bioadhesive compositions and processes for making the same. In one
embodiment, a bioadhesive composition includes dried distillers
solubles, which is derived from thin stillage.
[0019] In another embodiment, a method of making a bioadhesive
composition comprises evaporating at least a portion of water from
thin stillage obtained from a corn-to-ethanol fermentation process
to form condensed distillers solubles; drying the condensed
distillers solubles to form dried distillers solubles; and forming
a bioadhesive composition with the dried distillers solubles.
[0020] In another embodiment, a process for bonding one component
to another component comprises applying a bioadhesive composition
to a surface of at least one of the components, wherein the
bioadhesive composition comprises dried distillers solubles; and
contacting the one component with the other component, wherein the
bioadhesive composition is therebetween.
[0021] The disclosure may be understood more readily by reference
to the following detailed description of the various features of
the disclosure and the examples included therein.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0022] Referring now to the figures wherein the like elements are
numbered alike:
[0023] The FIGURE illustrates a process flow diagram for forming
the dried distillers solubles in accordance with the present
disclosure.
DETAILED DESCRIPTION
[0024] The present disclosure is generally directed to bioadhesives
derived from dried distillers solubles and methods for making the
same. The dried distillers solubles derive exclusively from the wet
processing stream of the corn-to-ethanol fermentation process and
can be comprised of water-soluble functionalized proteins, among
other constituents. As will be discussed in greater detail, the use
of dried distillers solubles in the bioadhesive composition
overcomes many of the problems noted in the prior art as it relates
to bioadhesives in general and as it relates to the prior art's use
of dried distillers grains. Moreover, because of the uniqueness of
the dried distillers solubles, the properties can be readily
manipulated by the use of additives and/or by compositional changes
as a function of processing and isolating the dried distillers
solubles. With regard to compositional changes, because the dried
distillers solubles is ultimately obtained from whole stillage
(i.e., the residue remaining after ethanol distillation), it should
be apparent that modification, physical or chemical, of the final
bioadhesive properties can be made to any one of the product
streams upstream from the dried distillers solubles as well as on
the dried distillers solubles itself.
[0025] For ease in understanding the present disclosure, it is
important to distinguish between dried distillers solubles and
dried distillers grains. As is well known in the art, the left over
byproducts of the corn-to-ethanol fermentation process are referred
to as whole stillage, which is generally the non-fermentable
grains, byproducts, and water that falls to the bottom of the
distillation column once the ethanol is distilled. The whole
stillage is typically mechanically treated (e.g., decanted,
centrifuged, pressed, or the like) to produce two fractions: a
substantially solids fraction referred to as wet distillers grains
and a substantially aqueous based fraction referred to as thin
stillage. The dried distillers solubles is derived from the
substantially aqueous based thin stillage fraction and will include
a relative high amount of water soluble proteins, which provides
many unique properties.
[0026] The thin stillage can be concentrated by use of evaporators
to produce condensed distillers solubles (also referred to as thin
stillage concentrate, or thin stillage syrup), which may be further
treated to remove oil entrained therein. The condensed distillers
solubles, once obtained, is oftentimes mixed with the wet
distillers grains and further dried in a dryer to form dried
distillers grains, which may then be used as animal feed. In some
processes, the wet distillers grains may be dried without the
addition of the thin stillage concentrate to form a dried grain
product that is also referred to by those in the art as dried
distillers grains, which may still or may not have an appreciable
moisture content depending on the extent of drying.
[0027] The composition of the condensed distillers solubles can
vary depending on the processing facility, ethanol process, and
corn variety, growing season and post processing methods. However,
on a dry matter weight basis condensed distillers solubles
typically have about equal parts amino acids/proteins to fatty acid
materials. One facility reported a composition of condensed
distillers solubles as containing dry matter of 33.4% of which the
composition included crude protein of 20.8%, crude fat of 22.2%,
crude fiber of 2.8%, ADF of 2.3%, NDF of 4.3%, and ash of 9.2%.
[0028] In the present disclosure, at least a portion of the
condensed distillers solubles is further dried to produce dried
distillers solubles and employed in a bioadhesive composition, as
is, modified, or in combination with other components. The dried
distillers solubles may or may not have an appreciable moisture
content depending on the extent of drying. Applicants have
discovered that bioadhesives derived from the dried distillers
solubles provide excellent adhesive properties that can be readily
tailored for a variety of applications without the problems noted
with the use of dried distillers grains or the expense related to
the use of soybeans.
[0029] The dried distillers solubles resultant material by itself
is generally in a compactable powder or granular form and, in some
embodiments, can be used directly as an adhesive, wherein the dried
distillers solubles forms an adhesive layer between two components,
and by the usage of heat and pressure can be configured to flow and
cure to form an adhered product. Alternatively, aqueous solutions
of the dried distillers solubles and/or any dried distillers
solubles precursor or co-product can readily be made and applied at
a desired viscosity. Still further, the dried distillers solubles
based bioadhesive composition may further be compounded with other
materials, wet and/or dry, to provide desired properties for a
given application. The particular adhesive application is not
intended to be limited. By way of example only, the dried
distillers solubles bioadhesive can be used for its adhesive
properties in papers, wood veneers, in the production of wood and
agrifiber composite panels such as particleboard, medium density
fiber board (MDF), oriented strand board (OSB), laminated lumber
products, and the like.
[0030] The resultant dried distillers solubles material can also be
used as a resin extender, wherein the dried distillers solubles is
blended with another adhesive such as a soy protein based
bioadhesive, for example, to lower its cost and provide various
functional advantages in the final blend. As such, the dried
distillers solubles can be an adhesive or resin extender for
various resins currently used in the wood composites and paper
industry such as phenol formaldehyde, and other types of
resins.
[0031] Referring now to the FIGURE, process 100 illustrates a
method for forming dried distillers solubles from the
corn-to-ethanol fermentation process 110. After aqueous
fermentation of the starch within the corn to produce ethanol, the
ethanol 123 is removed in a distillation step 120 leaving behind an
aqueous mixture of post fermentation byproducts, i.e., whole
stillage (WS) 121. The whole stillage 121 is then separated in a
separation process 130 into two fractions: the wet distillers
grains (WDG) 131 and the thin stillage fraction (TS) 132. The thin
stillage feedstream 132 is then subjected to an evaporation process
140 to remove moisture content so as to form condensed distillers
solubles (CDS) 141. Typically, the thin stillage 132 is first fed
to an evaporator e.g., a multistage evaporator, to remove at least
a portion of the water contained therein, i.e., 1.sup.st removal:
evaporation. In ethanol production facilities, the evaporation
temperatures within the evaporator generally are in a range of
about 100 to about 230.degree. F., and more typically, in a range
of about 110 to about 200.degree. F. The condensed distillers with
solubles 141 can then be subjected to an oil removal process to
remove at least a portion of the oil contained therein so as to
form defatted condensed distillers solubles 142 (CDS-F). The amount
of oil that is removed can be used to modify the properties of the
condensed distillers solubles once dried, i.e., dried distillers
solubles.
[0032] Optionally, the condensed distillers solubles 141 and/or the
defatted condensed distillers solubles 142 can be further
evaporated in a second evaporation step to remove additional
moisture therein to form a super concentrated condensed distillers
solubles 151, which may also be subject to an oil removal step or
in the case of defatted condensed distillers solubles subjected to
an additional oil removal step to form defatted concentrated
distillers solubles. Further concentration and oil removal may be
continued as may be desired.
[0033] The amount of oil (fat) removed and the removal method are
not intended to be limited to any particular amount/process so long
as at least a portion is removed relative to thin stillage by
itself, wherein the amount removed can be used to tailor the
adhesive properties. In addition to the production of dried
distillers solubles 171 and its subsequent use as a bioadhesive,
the extracted corn oil itself can be used for various applications
including, but not limited to, production of biodiesel, thereby
transforming what was previously considered as a low value product
into a significant revenue stream for ethanol plant operator.
[0034] The condensed distillers solubles 141, concentrated
condensed distillers solubles 151, defatted condensed distillers
solubles 142, or defatted concentrated condensed distillers
solubles 152 or like feed streams can be subject to wet compounding
160, which includes wet mixing the feedstream with other
components, at least one of which may be a solution or water. In
this step, additional additives, described in more detail below,
can be incorporated to form a modified distillers solubles.
[0035] The condensed distillers solubles 141, concentrated
condensed distillers solubles 151, defatted condensed distillers
solubles 142, and/or defatted concentrated condensed distillers
solubles, as well as the corresponding wet compounded distillers
solubles can then be subjected to thermal drying at step 170,
individually or in various combinations, to further reduce the
moisture content therein to an amount suitable for forming the
dried distillers solubles 171 for the particular end application.
The dried distiller solubles 171 which may be used as is or may be
dry compounded with dry ingredients. Again, doing so can be used to
manipulate the final adhesive properties as may be desired for
different adhesive applications. For example, the adhesive
properties for a given application may desire tacky adhesion, e.g.,
a post-it note, or may require a more permanent bond, e.g.,
formation of particle board, or may require a permanent bond that
is water insensitive or may be hot melted. Likewise, bond strength
can be varied.
[0036] Table 1 provides a general comparison on a dry matter basis
of a condensed distillers solubles composition without oil
extraction and a condensed distillers solubles composition with at
least a portion of the oil removed. Reference to defatted condensed
distillers solubles is not intended to infer that oil is completely
removed from the dried distillers with solubles. In some
embodiments, it may be beneficial to subject the condensed
distillers solubles to multiple oil [and/or water] extraction steps
to further decrease and manipulate the amount of oil [and/or water]
contained in the dried distillers with solubles product material.
In most embodiments, the oil content in the dried distillers with
solubles product material is from 3 to 15% by weight although
higher or lower amounts of oil may be desired in certain
applications
TABLE-US-00001 TABLE 1 Condensed Partially Defatted Distillers
Condensed Distillers Solubles Solubles Protein (%) 18 21 Fat (%) 20
7 Carbohydrates (%) 48 56 Ash (%) 14 16 Total (%) 100 100
[0037] As demonstrated in Table 1, the amount of oil can easily be
varied, which can directly affect the final bioadhesive properties
once the condensed distillers solubles are dried to form the dried
distillers solubles.
[0038] In a similar manner, the other constituents defining the
dried distillers solubles composition can be varied. For example,
the thin stillage 132 or condensed distillers with solubles 141 can
be treated to remove a portion of the carbohydrates and/or a
portion of the proteins contained therein. For example, a portion
of the low molecular weight proteins, may be removed. Likewise,
non-fermented starch and carbohydrates can be removed or partially
removed to tailor the bioadhesive properties by CO.sub.2
extraction, additional fermentation, or the like. Still further,
upstream treatment may include filtration, membrane filtration or
centrifugation technologies to isolate and reduce additional
components such as the suspended solids (dines) or selected
dissolved solids as may be desired for different applications.
[0039] Alternatively, the dried distillers with solubles can be
treated as is or upstream to modify one or more of the constituents
within the composition. For example, the proteins and/or
carbohydrates can be functionalized with different materials to
provide further manipulation of the bioadhesive properties. By way
of example, protein modifications can include, for example,
treating proteins with an acid, base or other agent that alters the
structure of one or more of the amino acid side chains, which, in
turn, alters the character of the protein and/or amino acids. For
example, the high glutamine and asparagine of prolamines,
particularly zein from corn, provides a means for manipulating the
charge characteristics of the protein by deamidation, thereby
providing a wide range of hydrophobicity. In one embodiment,
deamidation involves mild acid catalyzed deamidation at a pH of
about 1 at temperatures from about 25.degree. C. to about
65.degree. C. for a period of time sufficient to accomplish the
desired level of deamidation. In some embodiments, acids that form
stable dispersions and are useful within these classes include,
without limitation, lactic acid, citric acid, malonic acid,
phosphoric acid, fumaric acid, maleic acid, maleic anhydride,
maleated propylenes, glutaric acid, transaconitic acid, acetic
acid, propionic acid, sorbic acid, cysteine and glycyl glycine. In
one embodiment, lactic acid in the form of polylactic acid is used.
In another embodiment, maleated propylenes, such as G-3003 and
G-3015 manufactured by Eastman chemicals are used.
[0040] The thin stillage and condensed distillers solubles
feedstreams have conventionally been viewed as low-value
by-products, i.e., waste products. Problematically, the chemical
and physical characteristics of condensed distillers with solubles
adversely affect (and dilute the value of) wet distillers grains
when combined therewith. The resulting product stream, the
precursor to dried distillers grains with solubles, has reduced
protein content and is stickier and less tolerant to spoilage than
it would be without addition of condensed distillers with solubles
following evaporation. Consequently, producers have to burn more
fossil fuel-derived natural gas to dry dried distillers grains with
solubles longer than would otherwise be required in order to
vaporize more water and to avoid handling and spoilage issues. Low
moisture content translates directly into extended storage life.
Producers have generally had little choice but to follow the
standard industry practice of combining condensed distillers with
solubles with wet distillers grains prior to drying for the want of
an economically and technically feasible alternative. An object of
this disclosure is to provide such an alternative and empower
producers to reduce these inefficiencies by diverting and
separately processing condensed distillers with solubles. As a
result, the wet distillers grains does not require the extended
drying times since spoilage as a function of moisture content is
less of a concern.
[0041] Thin stillage and its more concentrated form of concentrated
distillers solubles form are generally comprised of water, protein,
fat, carbohydrates, ash, and relatively minor amounts of other
fermentation byproducts. At least some of the protein in the
feedstream has been hydrolyzed as a function of the fermentation
process conditions and is water-soluble. The fat is substantially
comprised of glycerides and is present in a free, bound and/or
emulsified state. The carbohydrate fraction is further comprised of
various sugars, partially-hydrolyzed starch, and insoluble
polysaccharides (cellulose, hemicellulose and lignin). Ash includes
residual minerals. Fermentation byproducts include glycerol, lactic
acid, acetic acid, yeast, and the like.
[0042] By the time concentrated distillers solubles exits the
evaporators, its protein and other constituents have changed
significantly due to continuous treatment during the fermentation
process with hot water, enzymes, caustic, acid, urea and/or other
chemicals, at times under pressure and/or vacuum, for more than two
days. Many of these process conditions are severe and are generally
known to facilitate at least some degree of hydrolysis,
denaturation and other presently favorable reactions and
reactants.
[0043] By way of example, ethanol facilities using the method
taught by Winsness in U.S. patent application Ser. No. 11/908,891
incorporated herein by reference in its entirety, iteratively wash
the whole stillage with at least a portion of the thin stillage
after initial separation of whole stillage into wet distillers
grains and thin stillage. This step increases the content of lower
density, low molecular weight and soluble components in the thin
stillage to enhance derivative co-product value, e.g., dried
distiller solubles. Moreover, as disclosed by Winsness, fat removal
efficiencies can be optionally increased by chemical addition
and/or by increasing temperature and/or concentrated thin stillage
or concentrated distillers solubles residence time at targeted
temperatures. Using such methods, concentrated distillers solubles
might be held at an elevated temperature for an extended period of
time at a pH of, for example, 3.5 to 4.5, before removing at least
some fat (oil) and directing the condensed distillers solubles for
final evaporation.
[0044] The dried distillers solubles is produced by introducing the
liquid feedstream into a drying gas stream and recovering the dried
distillers solubles from the drying gas stream. An exemplary
process is a high temperature pulse combustion process as described
in U.S. Pat. No. 7,937,850 to Tate et al., incorporated herein by
reference in its entirety. In this process, the condensed
distillers solubles are introduced into the drying gas stream at a
temperature of about 600.degree. F. to about 1800.degree. F.
[0045] In another embodiment, the dried distillers solubles is
obtained using a low temperature process. In this manner, the
proteins contained within the dried distillers solubles are
subjected to a less thermally aggressive process relative to the
preceding pulse combustion process and as a result, less denaturing
of the proteins and oxidation of the various constituents contained
within the feedstream may occur. In this method, some or all of the
liquid feedstream is conducted to a vessel or vessels for thermal
treatment, with or without one or more additive(s) in one or more
sequential stages under proscribed conditions and times. The vessel
or vessels used in this method can be operated in batch or
continuous fashion, and can incorporate one or more devices for
accomplishing thermal treatment by convection, conduction and/or
radiation, in sequence and/or concurrently.
[0046] The low temperature drying process applied can be applied to
the liquid fraction, e.g., thin stillage, condensed distillers
solubles, defatted condensed distillers solubles, and the like and
generally includes a fluidized bed apparatus configured to heat the
liquid fraction e.g., CDS (or thin stillage) to a temperature less
than 300.degree. F. in most embodiments, less than 250.degree. F.
in other embodiments, and less than 200.degree. F. in still other
embodiments. In one embodiment, the drying process is configured to
provide the DDS in a powder and/or granular form with a moisture
content of about 3 to about 20% by weight, and in other
embodiments, about 5 to about 12% by weight. The various additives
can be added by wet mixing prior to the drying process or dry
mixing.
[0047] In another embodiment, the dried distillers solubles is
obtained using a low temperature process. In this manner, the
proteins contained within the DDS are subjected to a less thermally
aggressive process relative to the preceding pulse combustion
process and as a result, less denaturing of the proteins and
oxidation of the various constituents contained within the
feedstream may occur. In this method, some or all of the liquid
feedstream is conducted to a vessel or vessels for thermal
treatment, with or without one or more additive(s) in one or more
sequential stages under proscribed conditions and times. The vessel
or vessels used in this method can be operated in batch or
continuous fashion, and can incorporate one or more devices for
accomplishing thermal treatment by convection, conduction and/or
radiation, in sequence and/or concurrently.
[0048] In an exemplary mode of this method, the liquid feedstream
is conducted through one or more nozzles into a manifold at the top
of vessel or vessels comprising an initial stage of thermal
treatment ("TT1"). A gas or gasses are simultaneously fed into TT1
through one or more inlets, at flow rates and temperatures that are
metered to precisely control intermediate temperature, residence
time and other relevant process variables such that, for example,
moisture is removed while avoiding undesirable particle deformation
or reactions. In an alternative embodiment, TT1 may also
incorporate use of a fluidized bed ("FB1") at the base of the TT1
vessel or vessels, into which a gas or gases are fed at rates and
temperatures sufficient to achieve incipient fluidization and, as
desired, to facilitate heat and/or mass transfer, reactions and/or
other relevant process objectives during TT1. The temperatures and
process conditions used in this process can be configured to
maintain the DDS product material during drying at a temperature
less than 300.degree. F. in most embodiments, less than 250.degree.
F. in other embodiments, and less than 200.degree. F. in still
other embodiments.
[0049] Another aspect involves further conveyance of the
intermediate feedstream from TT1 into a single or plurality of
additional thermal treatment zones (TT2, TT3 and so on), each
incorporating a means of convection, conduction and/or radiation to
achieve desired process objectives. In one method, such stage or
stages incorporate a fluidized bed (FB2, FB3 and so on), into which
a gas or gases are fed at rates and temperatures as may be
sufficient to, for example, gently heat and/or cool the
intermediate at iteratively lower temperatures. Air adjusted weirs
can be additionally incorporated into the method to manage
residence times.
[0050] Alternatively, the drying apparatus may be configured to
supplement the convective processes with conductive processes, such
as by incorporating an induction heater or intercooler into the
base of a fluid bed. Emissive methods can also be incorporated,
such as by adding infrared energy emitters into the housing walls,
or by adding a zone in which the feed material is treated by
electromagnetic radiation at wavelengths, intensities and times
sufficient to gently heat the interior of particles to enable more
efficient, lower temperature convection while avoiding excessive
surface dehydration and degradation, or other adverse reactions
that could impair functionality.
[0051] By way of a further example, any of the foregoing thermal
treatment methods could optionally involve introduction of one or
more additives, which may include liquid feedstream or any
co-product from a prior or subsequent stage of this invention or
the fermentation facility, during any stage of thermal treatment to
regulate the characteristics as desired to, for example, prevent
degradation or otherwise render the resulting DDS suitable for
further processing and/or its anticipated end use.
[0052] The thermal treatment processes described above may also be
utilized to facilitate targeted reactions, such as
functionalization, polymerization, crosslinking and the like, as
may be necessary to condition the DDS for its intended end use.
[0053] Other thermal treatment method can be used to supplement
convective processes with conductive methods, such as by
incorporating an induction heater or intercooler into the base of a
fluid bed. Emissive methods can also be incorporated, such as by
exposing the liquid fraction to infrared energy emitters, or by
adding a zone in which the liquid feed material is treated by
electromagnetic radiation at wavelengths, intensities and times
sufficient to gently heat the interior of particles to enable more
efficient, lower temperature convection while avoiding excessive
surface dehydration and degradation, or other adverse reactions
which could impair functionality.
[0054] By way of a further example, any of the foregoing thermal
treatment methods could optionally involve introduction of one or
more additives, which may include liquid feedstream or any
co-product from a prior or subsequent stage of this invention,
during any stage of thermal treatment to regulate the
characteristics as desired to, for example, prevent degradation or
otherwise render the resulting dried distillers solubles suitable
for further processing and/or its anticipated end use. Any additive
can be incorporated in a finishing step of dry compounding.
[0055] The drying thermal treatment processes described above may
also be utilized to facilitate targeted reactions, such as
functionalization, polymerization, crosslinking and the like, as
may be necessary to condition the dried distillers solubles for its
intended end use.
[0056] The dried distillers solubles and/or derivative or any of
the upstream intermediate product feedstreams including, but not
limited to, whole stillage, thin stillage, condensed distillers
solubles, defatted condensed distillers soluble, and the like, can
comprise at least another component, to manipulate the properties
of the bioadhesive such as, but not limited to, improving and/or
controlling the viscosity, adhesive properties, shelf-life, and
stability. Non-limiting examples of additional components include
tackifiers, plasticizers (plasticizing oils or extender oils),
waxes, antioxidants, UV stabilizers, colorants or pigments,
fillers, flow aids, biocides, lubricants, water, oil, coupling
agents, crosslinking agents, surfactants, catalysts solvents,
hydrolyzing agents, and combinations thereof. The foregoing
additives can be incorporated before or after drying thermal
treatment.
[0057] In some embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein can comprise a tackifier or tackifying resin or tackifier
resin. The tackifier may modify the properties of the composition
such as viscoelastic properties (e.g., tan delta), rheological
properties (e.g., viscosity), tackiness (i.e., ability to stick),
pressure sensitivity, and wetting property. In some embodiments,
the tackifier is used to improve the tackiness of the composition.
In other embodiments, the tackifier is used to reduce the viscosity
of the composition. In further embodiments, the tackifier is used
to render the composition a pressure-sensitive adhesive. In
particular embodiments, the tackifier is used to wet out adherent
surfaces and/or improve the adhesion to the adherent surfaces.
[0058] Any tackifier known to a person of ordinary skill in the art
may be used and is generally added to the bioadhesive composition
as opposed to upstream feedstreams. Tackifiers suitable for the
compositions disclosed herein can be solids, semi-solids, or
liquids at room temperature. Non-limiting examples of tackifiers
include (1) natural and modified rosins (e.g., gum rosin, wood
rosin, tall oil rosin, distilled rosin, hydrogenated rosin,
dimerized rosin, and polymerized rosin); (2) glycerol and
pentaerythritol esters of natural and modified rosins (e.g., the
glycerol ester of pale, wood rosin, the glycerol ester of
hydrogenated rosin, the glycerol ester of polymerized rosin, the
pentaerythritol ester of hydrogenated rosin, and the
phenolic-modified pentaerythritol ester of rosin); (3) copolymers
and terpolymers of natured terpenes (e.g., styrene/terpene and
alpha methyl styrene/terpene); (4) polyterpene resins and
hydrogenated polyterpene resins; (5) phenolic modified terpene
resins and hydrogenated derivatives thereof (e.g., the resin
product resulting from the condensation, in an acidic medium, of a
bicyclic terpene and a phenol); (6) aliphatic or cycloaliphatic
hydrocarbon resins and the hydrogenated derivatives thereof (e.g.,
resins resulting from the polymerization of monomers consisting
primarily of olefins and diolefins); (7) aromatic hydrocarbon
resins and the hydrogenated derivatives thereof; (8) aromatic
modified aliphatic or cycloaliphatic hydrocarbon resins and the
hydrogenated derivatives thereof; and combinations thereof.
[0059] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise or incorporate a plasticizer or
plasticizing oil or an extender oil that may reduce viscosity
and/or improve tack properties. Any plasticizer known to a person
of ordinary skill in the art may be used in the adhesion
composition disclosed herein. Non-limiting examples of plasticizers
include olefin oligomers, low molecular weight polyolefins such as
liquid polybutene, phthalates, mineral oils such as naphthenic,
paraffinic, or hydrogenated (white) oils (e.g. Kaydol oil),
vegetable and animal oil and their derivatives, petroleum derived
oils, and combinations thereof. In some embodiments, the
plasticizers include polypropylene, polybutene, hydrogenated
polyisoprene, hydrogenated polybutadiene, polypiperylene and
copolymers of piperylene and isoprene, and the like having average
molecular weights between about 350 and about 10,000. In other
embodiments, the plasticizers include glyceryl esters of the usual
fatty acids and polymerization products thereof.
[0060] In some embodiments, a suitable insoluble plasticizer may be
selected from the group which includes dipropylene glycol
dibenzoate, pentaerythritol tetrabenzoate; polyethylene glycol
400-di-2-ethylhexoate; 2-ethylhexyl diphenyl phsophate; butyl
benzyl phthalate, dibutyl phthalate, dioctyl phthalate, various
substituted citrates, and glycerates.
[0061] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise a wax that may reduce the melt
viscosity in addition to reducing costs. Any wax known to a person
of ordinary skill in the art can be used in the adhesion
composition disclosed herein. Non-limiting examples of suitable
waxes include petroleum waxes, polyolefin waxes such as low
molecular weight polyethylene or polypropylene, synthetic waxes,
paraffin and microcrystalline waxes having melting points from
about 55 to about 110.degree. C., Fischer-Tropsch waxes and
combinations thereof. In some embodiments, the wax is a low
molecular weight polyethylene homopolymer or interpolymer having a
number average molecular weight of about 400 to about 6,000
g/mole.
[0062] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise an antioxidant or a stabilizer. Any
antioxidant known to a person of ordinary skill in the art may be
used in the adhesion composition disclosed herein. Non-limiting
examples of suitable antioxidants include amine-based antioxidants
such as alkyl diphenylamines, phenyl-a-naphthylamine, alkyl or
aralkyl substituted phenyl-.alpha.-naphthylamine, alkylated
p-phenylene diamines, tetramethyl-diaminodiphenylamine and the
like; and hindered phenol compounds such as
2,6-di-t-butyl-4-methylphenol;
1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)benzene;
tetrakis (methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane
(e.g., IRGANOX.TM. 1010, from Ciba Geigy, N.Y.);
octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX.TM.
1076, commercially available from Ciba Geigy) and combinations
thereof.
[0063] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise an UV stabilizer that may prevent or
reduce the degradation of the compositions by UV radiation. Any UV
stabilizer known to a person of ordinary skill in the art may be
used in the adhesion composition disclosed herein. Non-limiting
examples of suitable UV stabilizers include benzophenones,
benzotriazoles, aryl esters, oxanilides, acrylic esters,
formamidine, carbon black, hindered amines, nickel quenchers,
hindered amines, phenolic antioxidants, metallic salts, zinc
compounds and combinations thereof.
[0064] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise a colorant or pigment. Any colorant
or pigment known to a person of ordinary skill in the art may be
used in the adhesion composition disclosed herein. Non-limiting
examples of suitable colorants or pigments include inorganic
pigments such as titanium dioxide and carbon black, phthalocyanine
pigments, and other organic pigments.
[0065] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise a filler. Any filler known to a
person of ordinary skill in the art may be used in the adhesion
composition disclosed herein. Non-limiting examples of suitable
fillers include sand, talc, dolomite, calcium carbonate, clay,
silica, mica, wollastonite, feldspar, aluminum silicate, alumina,
hydrated alumina, glass bead, glass microsphere, ceramic
microsphere, thermoplastic microsphere, barite, wood flour,
magnesium carbonate, calcium hydroxide, calcium oxide, magnesium
oxide, aluminum oxide, silicon oxide, iron oxide, boron nitride,
titanium oxide, talc, pyrophyllite clay, silicate pigment,
polishing powder, mica, sericite, bentonite, pearlite, zeolite,
fluorite, dolomite, quick lime, slaked lime, kaolin, chlorite,
diatomaceous earth, and combinations thereof.
[0066] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise a catalyst. Suitable catalysts
include without limitation, metallic catalysts and non-metallic
catalysts. Metal catalysts include, without limitation, metal
oxides, including, for example, zinc oxide, titanium dioxide,
copper oxides, (cuprous oxide and/or cupric oxide), aluminum oxide,
calcium oxide, stannous oxide, lead oxide and other metal oxides;
and metals, for example, zinc, titanium, copper, iron, nickel,
zirconium, and aluminum. Other catalysts include, without
limitation, fly ash and Portland cement.
[0067] Some oxides also assist with odor reduction and increase the
shelf life. Without being bound by theory, oxides, such as titanium
dioxide, may reduce auto-oxidation.
[0068] In further embodiments, the dried distillers solubles and/or
derivative or any of the upstream product feedstreams disclosed
herein optionally can comprise a crosslinker. Crosslinking agents
also have the ability to increase the mechanical and physical
performance of the present bioadhesive. As used herein,
crosslinking generally refers to linking at least two polymer
chains comprised, for example, of proteins, peptides,
polysaccharides, and/or synthetic polymers or the corn protein
material.
[0069] Suitable crosslinking agents include one or more of metallic
salts (e.g., NaCl or rock salt) and salt hydrates (which may
improve mechanical properties), urea, formaldehyde,
urea-formaldehyde, polyesters, phenol and phenolic resins,
melamine, methyl diisocyanide (MDI), polymeric methyl diphenyl
diisocyanate (pMDI), polymeric hexamethylene diisocyanate (pHMDI),
amine-epichlorohydrin adducts, epoxides, zinc sulfate, aldehydes
and urea-aldehyde resins epoxides, aldehyde, aldehyde starch,
dialdehyde starch, glyoxal, urea glyoxal, urea-aldehyde, polyamine
epichlorohydrin resin, polyamidoamine-epichlorohydrin resin,
polyalkylene polyamine-epichlorohydrin, amine
polymer-epichlorohydrin resin epoxy, resin mixtures, combinations
thereof, and the like. The same or similar agents may also serve as
binders.
[0070] The amine-epichlorohydrin adducts are defined as those
prepared through the reaction of epichlorohydrin with
amine-functional compounds. Among these are
polyamidoamine-epichlorohydrin resins (PAE resins),
polyalkylenepolyamine-epichlorohydrin (PAPAE resins) and amine
polymer-epichlorohydrin resins (APE resins). The PAE resins include
secondary amine-based azetidinium-functional PAE resins, tertiary
amine polyamide-based epoxide-functional resins and tertiary amine
polyamidourylene-based epoxide-functional PAE resins. It is also
possible to use low molecular weight amine-epichlorohydrin
condensates.
[0071] Additional additives can include a fiber additive. Suitable
fibers include any of a variety of natural and synthetic fibers.
Cellulose fibers include, without limitation, those from wood,
agricultural fibers, including flax, hemp, kenaf, wheat, soybean,
switchgrass, and grass, fibers obtained from paper and other fiber
recycling, including, without limitation, household and industrial
paper recycling streams, fibrous waste from the paper or wood
industries, including paper mill sludge. Synthetic fibers include
fiberglass, Kevlar, carbon fiber, nylon; mixtures or combinations
thereof, and the like. Mineral or silica additives may also be
used. The fiber can modify the performance of the biopolymers. For
example, longer fibers can be added to impart higher flexural and
rupture modulus to the cured or dried bioadhesive.
[0072] Nanomaterials may also be used as fillers, including
NanoCell (LDI Composites), which is a blend of cellulose, minerals
and clay that has been processed into a submicron material. It is
derived from paper mill sludge. NanoCell also contains small
percentages of metals and titanium dioxide. Other forms of
nanomaterials, such as nanofibers, nanotubes, nanocellulosics,
nanoclays and other forms of nanomaterials may also be included in
the dried distillers solubles biocomposite additive and/or the
biopolymer.
[0073] Other materials that can include components found in latex
paint, including, without limitation, latex compounds, including,
without limitation, acrylic latexes such as styrenated acrylic
latex; calcium carbonate, colorants, dispersants, such as, for
example, napthalene sulfonic acid condensation products; ammonium
hydroxide; surfactants; glycol ethers, including (propylene glycol)
methyl ether; 2,2,4-trimethylpentanediol-1,3-monoisobutyrate;
sodium nitrite; ethylene glycols, such as triethylene glycol
bis(2-ethylhexanoate); drying agents, such as metal oxides,
including, without limitation, zirconium oxides, cobalt oxides and
iron oxides, as well as ethylene oxides and ethylene oxide
derivatives and condensates, including, without limitation, fatty
alcohol ethoxylate, alkylphenol ethoxylate, fatty acid ethoxylate,
ethoxylated fatty amines, and the like; preservatives, emulsifiers
and thickeners.
[0074] Additional additives include citric acid including citric
acid monohydrate contains many carboxyl groups that are expected to
interact with both proteins and cellulosic based materials at
elevated temperatures.
[0075] The dried distillers solubles can also be dry blended with a
wide range of additional powder resin as a bioextender to either
lower the cost of the petrochemical resin powder or provide
functional advantages to the overall adhesive blend. Dried
distillers solubles can also be added to various formaldehyde
resins wherein the proteins can scavenge the residual formaldehyde
and increase the biobased content of the adhesive. Such powder or
liquid resins include but not limited to: phenol formaldehyde, urea
formaldehyde and melamine formaldehyde adhesives.
[0076] The following examples are presented for illustrative
purposes only, and are not intended to limit the scope of the
invention.
Example 1
[0077] In this example, condensed distillers solubles with at least
a portion of the oil removed was further evaporated in an
evaporator to a moisture content of about 50% by weight. The liquid
was then placed into a fluidized bed spray drier in which the
material was recirculated to provide a granular mixture. The
granular mixture was dried to two different moisture contents.
[0078] One sample had a moisture percentage of about 12% and the
other sample had a moisture content of 5% by weight The granular
material had a very light bright yellow color and emitted minimal
odor. The granular material was sandwiched between a particle board
and a wood veneer panel and heat pressed at 300.degree. F. and 10
pounds per square inch (psi). Once cooled to room temperature, the
veneer was qualitatively tested for adhesion by physically
attempting to separate the veneer from the particle board by hand.
In this example, the veneer panel could not be separated from the
particle board.
Example 2
[0079] In this example, the dried distillers solubles with at least
a portion of the oil removed in accordance with Example 1 was
blended with glycerine obtained from biodiesel production at a 50%
ratio and mixed. The material was used to laminate two kraft papers
together using heat and pressure.
Example 3
[0080] In this example, the dried distillers solubles with at least
a portion of the oil removed in accordance with Example 1 was
blended with water at a 1:1 ratio by weight and mixed. The material
was used to laminate two particle boards together. The sample was
clamped to maintain pressure for about 24 hours. The clamps were
removed and physical separation of the particle boards by hand was
not achieved, thereby indicating good adhesion.
Example 4
[0081] In this example, the dried distillers solubles with at least
a portion of the oil removed in accordance with Example 1 was
blended with water at a 1:1 ratio by weight and mixed. 5% Lactic
Acid was added and mixed. Then 5% magnesium oxide was added and
mixed. The material was used to laminate two particle boards
together. The sample was clamped to maintain pressure for about 24
hours. The clamps were removed and physical separation of the
particle boards by hand was not achieved, thereby indicating good
adhesion.
Example 5
[0082] In this example, the dried distillers solubles with at least
a portion of the oil removed in accordance with Example 1 was
blended with water at a 1:1 ratio by weight and mixed. 5% Ammonium
Polyphosphate was added and mixed. Then 5% magnesium oxide was
added and mixed. The material was used to laminate two particle
boards together. The sample was clamped to maintain pressure for
about 24 hours. The clamps were removed and physical separation of
the particle boards by hand was not achieved, thereby indicating
good adhesion.
Example 6
[0083] In this example, the dried distillers solubles with at least
a portion of the oil removed in accordance with Example 1 was
blended with water at a 1:1 ratio by weight and mixed. Separately,
a magnesium chloride solution was made with 25 parts of hydrated
magnesium chloride mixed with 15 parts water and mixed, then 60
parts of magnesium oxide was added to create the magnesium chloride
solution. 10% of the magnesium chloride solution was then added
with the aqueous solution containing the dried distillers solubles
and mixed. This material was used to laminate 2 layers of kraft
paper together.
[0084] This written description uses examples to disclose the
invention, including the best mode, and also to enable any person
skilled in the art to make and use the invention. The patentable
scope of the invention is defined by the claims, and may include
other examples that occur to those skilled in the art. Such other
examples are intended to be within the scope of the claims if they
have structural elements that do not differ from the literal
language of the claims, or if they include equivalent structural
elements with insubstantial differences from the literal languages
of the claims.
* * * * *