U.S. patent application number 10/980927 was filed with the patent office on 2005-03-24 for methods of producing compounds from plant material.
Invention is credited to Alderson, Eric V., Alnajjar, Mikhail S., Franz, James A., Frye, John G. JR., Neuenschwander, Gary G., Orth, Rick J., Schmidt, Andrew J., Werpy, Todd A., Zacher, Alan H..
Application Number | 20050064560 10/980927 |
Document ID | / |
Family ID | 32926649 |
Filed Date | 2005-03-24 |
United States Patent
Application |
20050064560 |
Kind Code |
A1 |
Werpy, Todd A. ; et
al. |
March 24, 2005 |
Methods of producing compounds from plant material
Abstract
The invention includes methods of processing plant material by
adding water to form a mixture, heating the mixture, and separating
a liquid component from a solid-comprising component. At least one
of the liquid component and the solid-comprising component
undergoes additional processing. Processing of the solid-comprising
component produces oils, and processing of the liquid component
produces one or more of glycerol, ethylene glycol, lactic acid and
propylene glycol. The invention includes a process of forming
glycerol, ethylene glycol, lactic acid and propylene glycol from
plant matter by adding water, heating and filtering the plant
matter. The filtrate containing starch, starch fragments,
hemicellulose and fragments of hemicellulose is treated to form
linear poly-alcohols which are then cleaved to produce one or more
of glycerol, ethylene glycol, lactic acid and propylene glycol. The
invention also includes a method of producing free and/or complexed
sterols and stanols from plant material.
Inventors: |
Werpy, Todd A.; (West
Richland, WA) ; Schmidt, Andrew J.; (Richland,
WA) ; Frye, John G. JR.; (Richland, WA) ;
Zacher, Alan H.; (Kennewick, WA) ; Franz, James
A.; (Kennewick, WA) ; Alnajjar, Mikhail S.;
(Richland, WA) ; Neuenschwander, Gary G.;
(Burbank, WA) ; Alderson, Eric V.; (Kennewick,
WA) ; Orth, Rick J.; (Kennewick, WA) |
Correspondence
Address: |
WELLS ST. JOHN P.S.
601 W. FIRST AVENUE, SUITE 1300
SPOKANE
WA
99201
US
|
Family ID: |
32926649 |
Appl. No.: |
10/980927 |
Filed: |
November 3, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10980927 |
Nov 3, 2004 |
|
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|
10379299 |
Mar 3, 2003 |
|
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Current U.S.
Class: |
435/105 |
Current CPC
Class: |
C07C 29/00 20130101;
C07C 29/00 20130101; C11B 1/10 20130101; C07C 29/60 20130101; C07C
29/00 20130101; C08B 30/10 20130101; C07C 29/60 20130101; C07C
31/202 20130101; C07C 31/205 20130101; C07C 31/225 20130101 |
Class at
Publication: |
435/105 |
International
Class: |
C12P 019/02 |
Goverment Interests
[0001] The invention was made with Government support under
Contract DE-FC36-00G10596, A000, awarded by the U.S. Department of
Energy. The Government has certain rights in the invention.
Claims
1-26. (Cancelled).
27. The method of claim 32, further comprising: heating the mixture
during the mixing; and wherein the extracted material comprises one
or more sterols selected from the group consisting of campesterol,
campestanol, stigmasterol, sitosterol and sitostanol.
28. The method of claim 27 further comprising after the recovering
the solid-comprising portion, removing additional water from the
solid-comprising portion prior to the treating the solid-comprising
portion with the solvent, the removing additional water comprising
one or more of vacuum drying, air drying, rotary drying, and
pressing.
29. The method of claim 27 wherein the solvent is selected from the
group consisting of hexane, ethyl acetate, methylene chloride,
acetone and mixtures thereof.
30. The method of claim 27 wherein the treating the
solid-comprising portion with a solvent is a first extraction and
further comprising treating the solid-comprising portion with one
or more additional solvents in a series of independent extraction
steps, the independent extraction steps each utilizing a solvent
independently selected from the group consisting of hexane, etyl
acetate, methylene chloride, acetone and mixtures thereof.
31. The method of claim 27 wherein the heating the mixture
comprises heating from about 100.degree. C. to about 200.degree. C.
for a length of time between about 1 minute and about 2 hours.
32. A method of producing oils from plant material, comprising:
providing plant material; mixing the plant material with water to
form a mixture; recovering a solid-comprising portion of the
mixture by at least one of pressing, filtering and centrifuging;
treating the solid-comprising portion with a solvent to extract a
material comprising one or more oils: and after the treating,
collecting the solvent containing the material.
33. The method of claim 32 wherein the method is a continuous
process.
34. The method of claim 32 wherein the providing plant material
comprises providing destarched corn material.
35. The method of claim 32 wherein the one or more oils comprise
one or more of a sterol, a stanol, a tocopherol and a
triglyceride.
36. The method of claim 32 wherein the solvent is a first solvent,
the material is a first material, and further comprising: treating
the solid portion with a second solvent, the treating with the
second solvent extracting a second material from the solid portion;
and after the treating with the second solvent, collecting the
second solvent containing the second material.
37. The method of claim 36 further comprising combining the first
solvent containing the first material and the second solvent
containing the second material.
38. The method of claim 36 wherein the first solvent and the second
solvent are the same.
39. (Cancelled)
Description
TECHNICAL FIELD
[0002] The present invention pertains to methods of processing
plant material and methods of producing compounds from plant
material.
BACKGROUND OF THE INVENTION
[0003] Industrial processing of corn material and other plant
material currently produces primarily starch with an accompanying
large volume of fiber byproduct. Despite the presence of useful
components within the fiber byproduct, most of the fiber byproduct
is utilized only as a low value component in livestock feed. The
usefulness of the plant fiber byproduct is currently limited by a
lack of developed methods for processing the plant fiber material
to produce the useful compounds contained therein.
[0004] It would be desirable to develop methods of producing useful
compounds from plant materials.
SUMMARY OF THE INVENTION
[0005] In one aspect, the invention encompasses a method of
processing plant material. Depending upon the initial water
content, an amount of water can be added to the plant material to
form a mixture. The mixture is separated into a liquid component
and a solid-containing component. At least one of the liquid
component and the solid-containing component undergoes additional
processing. Processing of the solid component produces oils, and
processing of the liquid component produces one or more of ethanol,
glycerol, ethylene glycol propylene glycol and lactic acid.
[0006] In one aspect, the invention encompasses a process of
forming one or more of glycerol, ethylene glycol, lactic acid and
propylene glycol from plant matter. Water can be added to plant
matter as needed to form a mixture. The mixture is heated and
filtered and the filtrate is retained. The filtrate contains
hemicellulose, fragments of hemicellulose and starch. At least some
of the hemicellulose and fragments of the hemicellulose are
converted to diols, linear polyalcohols and/or lactic acid. At
least some of the linear polyalcohols are cleaved to produce one or
more of glycerol, ethylene glycol, propylene glycol and lactic
acid.
[0007] In one aspect, the invention encompasses a method of
recovering sterols. A material containing plant fiber can be mixed
with water to form a mixture. The mixture is heated and filtered to
produce a filtrate and a solid-containing portion. The
solid-containing portion is treated with one or more solvents to
extract a material containing one or more free or complexed
sterols, stanols or triglycerides.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Preferred embodiments of the invention are described below
with reference to the following accompanying drawings.
[0009] FIG. 1 is a flowchart diagram of a preliminary processing
method of the present invention.
[0010] FIG. 2 is a flowchart diagram of step 100 depicted in FIG.
1.
[0011] FIG. 3 is a flowchart diagram of a processing method of the
present invention.
[0012] FIG. 4 is a flowchart diagram of step 300 of the processing
method shown in FIG. 3.
[0013] FIG. 5 is a flowchart diagram of a particular processing
sequence of the present invention.
[0014] FIG. 6 is a flowchart diagram of step 800 of the processing
sequence shown in FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] The invention encompasses methods which can be utilized for
generating compounds from plant materials. A preliminary processing
method encompassed by the present invention is described with
reference to FIG. 1. In an initial solubilization step 100 of the
preliminary processing, plant material is at least partially is
solubilized. In a separation step 200, the plant material
solubilized in step 100 is separated into liquid and
solid-comprising components.
[0016] Step 100 of FIG. 1 is described in greater detail with
reference to FIG. 2. The plant material solubilization step 100
initially involves a plant material providing step 110. The plant
material provided in step 110 is not limited to a specific plant
type and can include, for example, material from one or more of
corn, soybean, rice, barley, oats, chicory, wheat, and sugar beet.
A mixture comprising the provided plant material and a liquid can
be formed in an optional mixture formation step 130. Preferably,
step 130 comprises the addition of water to form an aqueous mixture
having a final water content of from about 50% to about 90%, by
weight. Where the plant material provided in step 110 comprises a
water content within the desired range, step 130 can be
omitted.
[0017] Mixture formation step 130 can comprise forming the mixture
to have a pH of from about 1 to about 11, preferably from about 1.5
to about 6.0. Although the pH of the mixture will typically fall
within the desired range without adjustment after the addition of
water, it is to be understood that the pH of the resulting mixture
can be adjusted to fall within this range of pH by addition of one
or more of an acid and a base.
[0018] As shown in FIG. 2, providing plant material can optionally
comprise destarching the plant material in a destarching step 120.
The present invention encompasses methods that utilize both step
120 and step 130, methods that utilize only one of step 120 and
step 130, and methods that omit both step 120 and step 130. It is
to be understood that methods of the present invention can be used
to treat either destarched plant material or plant material that
has not undergone a destarching treatment.
[0019] For purposes of the present invention, destarched plant
material can comprise plant material which has at least some of the
original starch content removed. In particular aspects, destarched
plant material can have greater than or equal to about 80% of the
original starch content removed. Removal of starch from plant
material can be achieved by a variety of conventional methods known
to those of ordinary skill in the art. After the destarching step
120, the destarched plant material can be used in step 130 to form
an aqueous mixture of destarched plant material.
[0020] As shown in FIG. 2, a hydrolysis step 140 can be performed
during plant material solubilization. Hydrolysis step 140 can
hydrolyze at least some of the polysaccharides in the plant
material mixture. Hydrolysis step 140 can comprise, for example,
heating of the plant material. Step 140 can alternatively or
additionally comprise addition of an acid in an amount appropriate
to adjust the pH of the mixture to a pH of from about 1 to about 3.
Numerous acids are available for use in hydrolysis step 140 such
as, for example, sulfuric acid, carbonic acid, phosphoric acid,
lactic acid, nitric acid, acetic acid, hydrochloric acid, and
mixtures thereof.
[0021] In embodiments of the present invention where it is
desirable to selectively produce polysaccharides such as, for
example, partially-hydrolyzed hemicellulose, it is advantageous to
avoid addition of acid or base during solubilization step 100 of
the preliminary processing. When the solubilization step 100 is
performed utilizing an aqueous mixture comprising a pH between
about 1 and about 12 (preferably from about 1.5 to about 6.0),
greater than or equal to about 75% of hemicellulose comprised by
the mixture can be solubilized while predominantly retaining a
polymeric form throughout solubilization step 100.
[0022] The plant material mixture formed in step 130 can undergo
solubilization from between about 1 minute to about 2 hours,
preferably from between about 5 minutes to about 1 hour. Where acid
has not been added, the temperature during solubilization can be
from about 100.degree. C. to about 200.degree. C., preferably from
between about 120.degree. C. to about 180.degree. C., and more
preferably from about 140.degree. C. to about 160.degree. C. If
acid is added during step 140, the solubilization temperature can
be from about 100.degree. C. to about 200.degree. C., preferably
from 120.degree. C. to about 180.degree. C., and more preferably
from 120.degree. C. to 160.degree. C.
[0023] As shown in FIG. 1, a separation step 200 can be performed
after solubilization step 100. Separation step 200 can comprise,
for example, one or more of centrifugation, pressing, and
filtration. Separation step 200 can produce a liquid-comprising
portion or filtrate, and a solid-comprising component. The liquid
component 210 and the solid-comprising component 220 can
independently undergo further processing as discussed below.
[0024] The filtrate or liquid component produced by the separation
step 200 can comprise, for example, one or both of polysaccharides
and monosaccharides. As discussed above with respect to plant
material solubilization step 100 depicted in FIG. 2, the relative
amount of monosaccharides and polysaccharides present in the liquid
component will depend upon conditions utilized during the
solubilization step. The saccharides present in the liquid
component can comprise, for example, partially hydrolyzed starch,
partially hydrolyzed hemicellulose, polymeric fragments of
hemicellulose, and monosaccharide components of hemicellulose. The
filtrate can also comprise polysaccharides and monosaccharides of
non-hemicellulose origin such as, for example, monosaccharide and
polysaccharide breakdown products of starch and cellulose present
in the plant material. As shown generally in FIG. 3, liquid
component can be subjected to reduction step 400 to chemically
reduce at least some of the saccharides present in the
filtrate.
[0025] As indicated generally in FIG. 3, processing of the liquid
component 210 can comprise an initial processing step 300 prior to
saccharide reduction step 400. Step 300 is described in more detail
with reference to FIG. 4. The liquid portion of separation step 200
can be collected in liquid collection step 310 and a neutralization
step 320 can be performed if necessary, to adjust the pH of the
collected liquid to between about 3 and 8, preferably to a pH of
from about 4.5 to about 6.5. Neutralization step 320 can be
utilized, for instance, when the preceding processing comprises an
addition of acid. It can be advantageous to perform neutralization
step 320 prior to a reduction step 400 or a hydrogenolysis step 500
shown in FIG. 3 (discussed below) to alleviate or avoid
detrimentally effecting catalyst activity during the reduction or
hydrogenolysis.
[0026] Referring again to FIG. 4, the liquid collected in step 310
can optionally undergo a pretreatment step 330. As shown in FIG. 4,
pretreatment can occur prior to neutralization step 320.
Alternatively, pretreatment step 330 can be performed after
neutralization step 320. Pretreatment step 330 can comprise, for
example, at least one of ultra filtration, carbon filtration, anion
exchange chromatography, cation exchange chromatography, and a
treatment comprising chemical adjustment followed by precipitation
and subsequent separation, where chemical adjustment can include
but is not limited to affecting solubility by changing the pH or by
addition of a divalent cation. When pretreatment comprises ultra
filtration, the ultra filtration can comprise filtration using a
molecular weight cutoff filter size of from 2,500 to 50,000.
Pretreatment step 330 can remove greater than or equal to 90% of
any protein, hydrolyzed protein and/or amino acids present in the
liquid solution. It can be advantageous to remove protein from the
solution prior to subsequent reduction or hydrogenolysis steps
(discussed below) to alleviate or avoid detrimentally effecting or
deactivating a catalyst utilized in the reduction or the
hydrogenolysis.
[0027] In addition to the feature described above, the formation of
liquid component step 300 can optionally include a hydrolysis step
340. As shown in FIG. 4, hydrolysis step 340 can be utilized in
addition to pretreatment step 330 or can be utilized when
pretreatment step 330 is omitted. Where hydrolysis step 340 is
utilized in conjunction with pretreatment step 330, hydrolysis step
340 can occur prior to or subsequent to pretreatment step 330.
Hydrolysis step 340 can hydrolyze at least some of any
polysaccharides present in the liquid collected in step 310. In
some instances, it can be advantageous to perform hydrolysis step
340 to hydrolyze polysaccharides present in the solution and
thereby minimize any detrimental effect polysaccharides may have on
the activity of a catalyst used in subsequent processing steps.
[0028] Hydrolysis step 340 can comprise an addition of an acid or a
base. Preferably, hydrolysis step 340 utilizes an acid which can
comprise, for example, one or more of sulfuric acid, carbonic acid,
phosphoric acid, lactic acid, nitric acid, acetic acid,
hydrochloric acid, and mixtures thereof. It can be preferable in
some instances to use an acid other than sulfuric acid to alleviate
detrimental effects sulfate may have on catalysts utilized in
subsequent processing steps according to the present invention. In
embodiments utilizing acidic hydrolysis step 340, the pH of the
solution during the hydrolysis step can preferably be between about
pH 1 and about pH 5, and more preferably between about pH 1.5 and
pH 2.5.
[0029] An effective temperature for purposes of hydrolysis step 340
can be between from about 100.degree. C. to about 200.degree. C.,
preferably from about 120.degree. C. to about 160.degree. C., and
more preferably from between about 120.degree. C. through about
140.degree. C. It can be beneficial to perform hydrolysis step 340
to decrease the high temperature requirements during a subsequent
reduction step, discussed below. In embodiments of the present
invention where hydrolysis step 340 is utilized, neutralization
step 320 can comprise to readjustment of the pH of the liquid to
between about 3 and 7, preferably to a pH of from about 4.5 to
about 6.5, prior to subsequent processing steps.
[0030] Referring again to FIG. 3, initial processing of the liquid
component can be followed by reduction step 400. Reduction step 400
can comprise chemical reduction of saccharides by, for example,
hydrogenation conditions which can convert at least some of any
monosaccharides and polysaccharides present in the liquid component
into the respective linear polyalcohols. In addition, if
polysaccharides are present in the liquid component, hydrolysis to
form the respective monosaccharides can occur during the reduction
and can be enhanced by an increased reaction temperature.
[0031] Reduction step 400 can comprise catalytic hydrogenation.
Catalytic hydrogenation can comprise exposing saccharides to a
catalyst comprising a support and one or more members of the groups
consisting of Ru, Ni, Pt, and Pd. The catalyst support can comprise
carbon and/or other insoluble support material, such as titania and
zirconia. Catalytic hydrogenation can comprise a temperature from
about 80.degree. C. to about 300.degree. C., preferably from about
100.degree. C. to about 250.degree. C. and more preferably from
about 120.degree. C. to about 200.degree. C. A hydrogen pressure
during hydrogenation can be from about 100 psig H.sub.2 to about
3,000 psig H.sub.2, preferably from between about 1,000 psig
H.sub.2 and about 2,200 psig H.sub.2 and most preferably from about
1,200 psig H.sub.2 to about 1,800 psig H.sub.2. Hydrogenation can
be performed over a time range of from about 1 minute to about 8
hours, preferably from between about 1 minute and about 4
hours.
[0032] Hydrogenation according to methods of the present invention
can produce a total amount of linear polyalcohols which can
comprise sorbitol, xylitol and arabinitol as the major polyalcohols
present. Sorbitol can comprise from 0% to 100% of the total amount
of linear polyalcohols produced, xylitol can comprise from 0% to
100% of the total amount of linear polyalcohols produced, and
arabinitol can comprise from 0% to 100% of the total amount of
linear polyalcohols produced.
[0033] Referring again to FIG. 3, after the reduction of
saccharides in reduction step 400, the liquid component can be
subjected to a hydrogenolysis step 500. Hydrogenolysis step 500 can
cleave at least some of the linear polyalcohols produced by
reduction step 400 to form a group of products that can be
collected by collection step 600 (discussed below).
[0034] Hydrogenolysis step 500 can comprise catalytic
hydrogenolysis. Catalytic hydrogenolysis can utilize a catalyst
such as, for example, a catalyst comprising a support and one or
more members of the group consisting of Ru, Ni, Re, and Co. The
support can comprise for example, one or more of carbon, titania
and zirconia. Catalytic hydrogenolysis step 510 can further
comprise utilization of an added base. Assuming a neutral starting
pH of from about pH 5 to about pH 8, an appropriate pH for
catalytic hydrogenolysis step 510 can be achieved by, for example,
an addition sodium hydroxide to a final concentration of from about
0% to about 10% by weight, and preferably from about 0.5% to about
2% by weight, relative to the weight of the final solution.
[0035] As shown in FIG. 3, reduction reaction step 400 and
hydrogenolysis reaction step 500 can be performed individually.
Alternatively, the reduction reaction can be combined with
hydrogenolysis within a common reaction vessel (not shown) and can
utilize a common catalyst. For purposes of a combined
hydrogenation/hydrogenolysis, a common catalyst can be, for
example, Ru on a carbon support. The conditions for the combined
hydrogenation and hydrogenolysis reactions can comprise initial
conditions identical to the conditions discussed above with respect
to reduction reaction 400 as conducted independently. In the
combined reaction, hydrogenolysis can be induced by, for example,
an addition of sodium hydroxide into the common reaction chamber.
Assuming the solution was neutralized prior to the hydrogenation
conditions, sodium hydroxide can be added according to the
conditions discussed above with respect to hydrogenolysis reaction
step 500, as conducted independently. The appropriate amount of
sodium hydroxide to be utilized for hydrogenolysis reaction, either
as performed independently or as combined with reduction reaction
400, can be varied within the ranges discussed above based upon the
pH of the solution prior to addition of the base and the sugar
concentration in the solution.
[0036] As shown in FIG. 3, a product collection step 600 can be
performed after hydrogenolysis reaction 500 to collect a group of
products. The group of products can comprise one or more of lactic
acid, propylene glycol, ethylene glycol and glycerol. A combined
amount of ethylene glycol, propylene glycol and glycerol in the
liquid component after hydrogenolysis reaction 500 can comprise
from about 50% to about 100% of the total amount of carbon present
in the liquid component.
[0037] In addition to the features described above, methods of the
present invention can include processing of a solid-comprising
portion 220 obtained by the separation step 200 shown in FIG. 1.
Methods for processing of the solid-comprising portion according to
the present invention are discussed generally with reference to
FIG. 5. An initial processing step 700 can optionally be utilized
to remove at least some of any liquid portion present in the
solid-comprising component. Initial processing step 700 can
comprise removal of some or all of any water present in the
component utilizing one or more of filtration, air drying, vacuum
drying and heating. Alternatively, subsequent processing of the
solid-comprising component can be performed in an absence of any
further removal of liquid or additional drying.
[0038] As shown in FIG. 5, whether or not initial processing step
700 is performed, processing of the solid-comprising component can
include an extraction step 800. Extraction step 800 is discussed in
more detail with reference to FIG. 6. Extraction step 800 can
include a first solvent addition step 810. Numerous suitable
solvents are available for purposes of the extraction step, and can
include but are not limited to one or more of hexane, ethyl
acetate, methylene chloride, and acetone. Solvent can be added to
provide a volume to mass ratio of from about 1:1 to about 20:1,
where the volume is the volume of the added solvent and the mass is
the mass of the solid-comprising component prior to solvent
addition. In particular processing events, the volume to mass ratio
can preferably be about 10:1. The extraction can be conducted for a
time of from a few seconds to several hours. Additionally, the
extraction can be conducted batchwise or utilizing a continuous
process. Extraction step 800 can comprise a first solvent
separation step 820 to separate the first solvent from a
non-solubilized portion of the solid component. A collection step
830 can be utilized to collect a solubilized component in the
separated first solvent.
[0039] As shown in FIG. 6, the non-solubilized portion of solvent
separation step 820 can be retained in a retention step 840. An
optional second solvent addition step 850 can be performed and can
utilize the conditions discussed above with respect to the first
solvent addition. After a second solvent addition, a second solvent
separation step 860 can be performed and the second solvent portion
containing a second solubilized component can be recovered. The
second solubilized component can be combined with the first
solubilized component in a combination step 870 which combines the
solvent collected in step 830 with the solvent collected from
separation step 860. Alternatively the first solvent collected in
830 and the second solvent collected in 860 can remain separate. It
is to be noted that the solvent used for addition of solvent step
810 and the solvent used for the second solvent addition step 850
can be identical or can be different. Further, the first solvent
collected in step 830 can comprise a product material that is
different than the product material extracted by the second solvent
addition.
[0040] As shown in FIG. 6, extraction step 800 can comprise one or
two additions of solvent steps 810 and 850. It is to be understood
that the present invention can encompass methods utilizing greater
than two solvent addition steps (not shown). It can be advantageous
to utilize a plurality of solvent additions and separation steps to
maximize product extraction.
[0041] Referring again to FIG. 5, after extraction step 800, the
extracted products can be collected in a collection step 900. The
extracted products collected in step 900 can be from about 3% to
about 5% of the initial plant material by weight, or alternatively
up to 100% of available extractables. The extracted product can
comprise, for example, one or more of campesterol, campestanol,
stigmasterol, sitosterol, sitostanol, tocopherols and
triglycerides.
[0042] In compliance with the statute, the invention has been
described in language more or less specific as to structural and
methodical features. It is to be understood, however, that the
invention is not limited to the specific features shown and
described, since the means herein disclosed comprise preferred
forms of putting the invention into effect. The invention is,
therefore, claimed in any of its forms or modifications within the
proper scope of the appended claims appropriately interpreted in
accordance with the doctrine of equivalents.
* * * * *