U.S. patent application number 16/026492 was filed with the patent office on 2018-11-01 for treated biodiesel glycerin.
This patent application is currently assigned to Auburn University. The applicant listed for this patent is Auburn University. Invention is credited to Rodrigo Rodriguez-Kabana, Robert H. Walker.
Application Number | 20180310555 16/026492 |
Document ID | / |
Family ID | 39733593 |
Filed Date | 2018-11-01 |
United States Patent
Application |
20180310555 |
Kind Code |
A1 |
Rodriguez-Kabana; Rodrigo ;
et al. |
November 1, 2018 |
Treated Biodiesel Glycerin
Abstract
Disclosed are compositions that include treated biodiesel
glycerin. The disclosed compositions may be utilized as
soil-amendments for controlling pests, weeds and for enhancing
growth of plants. The biodiesel glycerin utilized in the disclosed
compositions may be treated by one or more steps including
neutralization, heating, refluxing, condensing, and distilling.
Inventors: |
Rodriguez-Kabana; Rodrigo;
(Auburn, AL) ; Walker; Robert H.; (Auburn,
AL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Auburn University |
Auburn |
AL |
US |
|
|
Assignee: |
Auburn University
Auburn
AL
|
Family ID: |
39733593 |
Appl. No.: |
16/026492 |
Filed: |
July 3, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15634667 |
Jun 27, 2017 |
10034475 |
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16026492 |
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15271550 |
Sep 21, 2016 |
9756854 |
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15634667 |
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14886374 |
Oct 19, 2015 |
9451766 |
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15271550 |
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14268381 |
May 2, 2014 |
9181139 |
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14886374 |
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13836460 |
Mar 15, 2013 |
8754134 |
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14268381 |
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12040484 |
Feb 29, 2008 |
8519009 |
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13836460 |
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60937243 |
Jun 26, 2007 |
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60964913 |
Aug 15, 2007 |
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60904672 |
Mar 2, 2007 |
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60937128 |
Jun 26, 2007 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 35/02 20130101;
Y02W 30/47 20150501; A01N 31/02 20130101; C05C 9/00 20130101; C05B
17/00 20130101; Y02E 50/30 20130101; Y02W 30/40 20150501; Y02E
50/343 20130101; C05G 3/60 20200201; A01N 31/02 20130101; A01N
35/02 20130101; A01N 37/46 20130101; A01N 47/28 20130101; A01N
63/10 20200101; A01N 31/02 20130101; A01N 35/02 20130101; A01N
37/46 20130101; A01N 47/28 20130101; A01N 63/10 20200101 |
International
Class: |
A01N 35/02 20060101
A01N035/02; C05C 9/00 20060101 C05C009/00; C05G 3/02 20060101
C05G003/02; A01N 31/02 20060101 A01N031/02; C05B 17/00 20060101
C05B017/00; A01N 37/46 20060101 A01N037/46; A01N 47/28 20060101
A01N047/28; A01N 63/02 20060101 A01N063/02 |
Claims
1. A soil-amendment composition for controlling soil-bourne pests,
the composition comprising: (a) an effective amount of a treated
crude glycerin composition, wherein the crude glycerin composition
is obtained as a by-product of a reaction mixture for producing
biodiesel fuel and the crude glycerin composition is treated by:
(i) adjusting the pH of the crude glycerin composition to about
4.0-6.8 to obtain a neutralized composition; and (ii) removing an
insoluble precipitate from the neutralized composition; thereby
obtaining the treated crude glycerin composition; and (b) an
effective amount of a nitrogen source; wherein the composition has
a molar ratio of total carbon to total nitrogen (C:N) of about
(22.4-5.6):1.
2. The soil-amendment composition of claim 1, wherein the crude
glycerin composition is further treated by: (iii) heating the
neutralized composition; and (iv) removing a volatile distillate
fraction from the neutralized composition; thereby obtaining the
treated crude glycerin composition.
3. The soil-amendment composition of claim 2, wherein the crude
glycerin composition is further treated by: (v) refluxing the
neutralized composition; and (vi) distilling and collecting a
volatile distillate fraction; thereby obtaining the treated crude
glycerin composition.
4. The composition of claim 1, wherein the soil-bourne pests are
parasitic nematodes.
5. The composition of claim 1, wherein the composition is effective
for reducing parasitic nematodes by at least about 50% when applied
at an application rate of about 1 ml/kg soil.
6. The composition of claim 1, wherein the composition does not
reduce microbivorous nematodes by more than about 50% when applied
at an application rate of about 1 ml/kg soil.
7. The composition of claim 1, wherein the reaction mixture for
producing biodiesel fuel comprises: (a) animal fat, vegetable oil,
or a mixture thereof; (b) a base, wherein the reaction mixture has
a pH of at least about 11; and (c) an alcohol selected from a group
consisting of methanol, ethanol, and a mixture thereof.
8. The composition of claim 7, wherein the base is selected from
the group consisting of NaOH, KOH, NaOCH.sub.3 and KOCH.sub.3.
9. The composition of claim 1, wherein prior to being treated the
crude glycerin composition comprises: (a) about 65-85% glycerin;
(b) acrolein; (c) monoglycerides; and (d) alcohol; and the crude
glycerin composition has a pH of greater than about 11.
10. The composition of claim 1, wherein the treated crude glycerin
composition comprises: (a) about 65-85% glycerin; (b) acrolein; and
(c) no more than about 5% monoglycerides.
11. The composition of claim 2, wherein the treated crude glycerin
composition comprises: (a) about 65-85% glycerin; (b) acrolein; and
(c) no more than about 5% alcohol.
12. The composition of claim 3, wherein the treated crude glycerin
composition comprises: (a) about 65-85% glycerin; and (b) at least
about 5% acrolein.
13. The composition of claim 1, wherein adjusting the pH of the
crude glycerin composition to about 4.0-6.8 comprises adding acid
to the composition.
14. The composition of claim 13, wherein the acid is an organic
acid.
15. The composition of claim 14, wherein the organic acid is a
carboxylic acid selected from a group consisting of acetic acid,
propionic acid, butyric acid, valeric acid or a mixture
thereof.
16. The composition of claim 13, wherein the acid is an inorganic
acid selected from a group consisting of phosphoric acid and
sulfuric acid.
17. The composition of claim 13, wherein the acid is a mixture of a
carboxylic acid and phosphoric acid.
18. The composition of claim 2, wherein heating comprises heating
the neutralized composition to a temperature of at least about
90.degree. C. under vacuum.
19. The composition of claim 3, wherein refluxing comprises heating
the neutralized composition to a temperature of about
200-300.degree. C.
20. The composition of claim 1, wherein the nitrogen source
comprises urea, casein, or a mixture thereof.
21. The composition of claim 1, wherein the crude glycerin
composition further is treated by reacting the composition with
sodium bisulfate or potassium bisulfate.
22. The composition of claim 1, further comprising sulfur.
23. A method for preparing a soil-amendment composition for
controlling soil-bourne pests, the method comprising combining: (a)
an effective amount of a treated crude glycerin composition,
wherein the crude glycerin composition is obtained as a by-product
of a reaction mixture for producing biodiesel fuel and the crude
glycerin composition is treated by: (i) adjusting the pH of the
crude glycerin composition to about 4.0-6.8 to obtain a neutralized
composition; and (ii) removing an insoluble precipitate from the
neutralized composition; thereby obtaining the treated crude
glycerin composition; and (b) an effective amount of an organic
nitrogen source; wherein the composition has a molar ratio of total
carbon to total nitrogen (C:N) of about (22.4-5.6):1.
24. A method for preparing a soil-amendment composition for
controlling soil-bourne pests, the method comprising: (a) adjusting
the pH of a crude glycerin composition to about 4.0-6.8 to obtain a
neutralized composition; wherein the crude glycerin composition is
obtained as a by-product of a reaction mixture for producing
biodiesel fuel; (b) removing an insoluble precipitate from the
neutralized composition, thereby obtaining a treated crude glycerin
composition; and (c) combining an effective amount of the treated
crude glycerin composition and an effective amount of an organic
nitrogen source such that the composition has a molar ratio of
total carbon to total nitrogen (C:N) of about (22.4-5.6):1.
25. A method for controlling soil-bourne pests comprising applying
a liquid soil-amendment composition at an application rate of at
least about 1 ml/kg soil, the soil-amendment composition
comprising: (a) an effective amount of a treated crude glycerin
composition, wherein the crude glycerin composition is obtained as
a by-product of a reaction mixture for producing biodiesel fuel and
the crude glycerin composition is treated by: (i) adjusting the pH
of the crude glycerin composition to about 4.0-6.8 to obtain a
neutralized composition; and (ii) removing an insoluble precipitate
from the neutralized composition; thereby obtaining the treated
crude glycerin composition; and (b) an effective amount of an
organic nitrogen source; wherein the composition has a molar ratio
of total carbon to total nitrogen (C:N) of about (22.4-5.6):1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn. 119(e) to prior U.S. provisional application No.
60/904,672, filed on Mar. 2, 2007; application No. 60/937,128,
filed on Jun. 26, 2007; application No. 60/937,243, filed on Jun.
26, 2007; and application No. 60/964,913, filed on Aug. 15, 2007;
the contents of which are incorporated by reference herein in their
entireties.
BACKGROUND
[0002] The field of the invention relates to glycerin by-products
of biodiesel fuel production. In particular, the field of the
invention related to the use of treated glycerin by-products of
biodiesel fuel production as soil-amendments.
[0003] Biodiesel fuels (BDF) are important sustainable energy
sources. They are available commercially for use as alternatives
for replacement of fuels derived from coal, petroleum, and other
fast dwindling and non-renewable fossil energy sources. BDF usually
are esters of fatty acids with simple alcohols, principally
methanol. The production of fatty acids for BDF manufacture may be
based on a transesterification reaction of sodium methylate with
animal or vegetable fats, which are esters of acids with glycerin
(1,2,3-propanetriol). This is followed by separation of glycerin
and other impurities from the methylated fatty acids, usually based
on the fact that glycerin has a higher density than methylated
fatty acids and sinks to the bottom of a batch reaction mixture.
The BDF process thus results in accumulation of significant
quantities of crude glycerin as by-product (ie., "BDF
glycerin").
[0004] BDF glycerin commonly contains about 65-85% glycerin and
other impurities that include acrolein, monoglycerides, and "high
boiling compounds." Production of commercial-grade glycerin, which
is usually about 90-95% glycerin, requires removal of these
impurities for potential markets. The increased cost of
purification and the surfeit of glycerin in the world market today
translate into a serious disposal problem for this by-product of
BDF manufacture. Most crude glycerin today often is sold for
burning as a source of energy. The oversupply of glycerin is
considered one of the major problems in development of the
biodiesel industry and new compositions and uses for BDF glycerin
are desirable.
SUMMARY
[0005] Disclosed are compositions that comprise treated crude
glycerin that is obtained as a by-product of methods for producing
biodiesel fuel. The disclosed compositions may be useful as
soil-amendments for controlling pests, controlling weeds, or
enhancing growth of crops as a fertilizer. The disclosed
composition may be utilized as soil-amendments either alone or in
combination with additional ingredients.
[0006] In some embodiments, the disclosed compositions are utilized
as soil-amendment compositions for controlling soil-bourne pests,
weeds, or both, and comprise: (a) an effective amount of a treated
crude glycerin composition, where the crude glycerin composition is
obtained as a by-product of a reaction mixture for producing
biodiesel fuel and the crude glycerin composition is treated by:
(i) adjusting the pH of the crude glycerin composition to about
4.0-6.8 (preferably 5.5-6.8, and more preferably 5.8-6.5) to obtain
a neutralized composition; and (ii) removing an insoluble
precipitate from the neutralized composition; thereby obtaining the
treated crude glycerin composition; and optionally (b) an effective
amount of an nitrogen source (e.g., an organic or inorganic
nitrogen source); where the composition has a molar ratio of total
carbon to total nitrogen (C:N) of about (22.4-5.6):1, and
preferably about (16.8-11.2):1. In further embodiments, the crude
glycerin composition is further treated by: (iii) performing one or
more steps that include heating, refluxing, condensing, or
distilling the neutralized composition; and optionally (iv)
removing or collecting a volatile distillate fraction; thereby
obtaining the treated crude glycerin composition.
[0007] The disclosed compositions may be utilized as soil-amendment
compositions for controlling soil-bourne pests, weeds, or both. In
some embodiments, the soil-bourne pests are parasitic nematodes
such as Rotylenchulus reniformis. In some embodiments, the
disclosed compositions may be effective for reducing parasitic
nematodes populations in amended soil by at least about 50%
(preferably by at least 60%, 70%, 80%, or 90%) when applied at an
application rate of about 1 ml/kg soil (or optionally at a higher
rate of about 2 ml/kg soil, 3 ml/kg soil, or 4 ml/kg soil). In
further embodiments, the disclosed compositions may not have a
significantly detrimental effect on beneficial nematodes. For
example, in some embodiments the disclosed compositions do not
reduce beneficial microbivorous nematodes in amended soil by more
than about 50% (preferably by no more than least 40%, 30%, 20%, or
10%) when applied at an application rate of about 1 ml/kg soil (or
optionally at a higher rate of about 2 ml/kg soil, 3 ml/kg soil, or
4 ml/kg soil).
[0008] The crude glycerin utilized to prepare the disclosed
compositions may be obtained as a by-product of a reaction mixture
for producing biodiesel fuel (e.g., a reaction mixture for
producing alkyl esters of fatty acids via transesterification). The
reaction mixture for producing biodiesel fuel may include: (a)
animal fat, vegetable oil, or a mixture thereof; (b) a base,
wherein the reaction mixture has a pH of at least about 11; and (c)
an alcohol. Suitable bases may include, but are not limited to,
metal hydroxides (e.g., NaOH and KOH), metal alkoxides (e.g.,
NaOCH.sub.3 and KOCH.sub.3), and mixtures thereof. In some
embodiments, the base is a potassium salt (e.g., KOH, KOCH.sub.3,
or mixture thereof). Suitable alcohols may include, but are not
limited to, aliphatic alcohols such as methanol, ethanol, or a
mixture thereof.
[0009] The crude glycerin utilized to prepare the disclosed
compositions includes glycerin (e.g., at a concentration of about
65-85%) and may include additional components, which may include,
but are not limited to, enal compounds (e.g., acrolein or
"2-propenal"), residual glycerides (e.g., monoglycerides), and
residual volatiles (e.g., alcohol such as methanol or ethanol). The
crude glycerin typically is treated prior to being utilized to
prepare the disclosed composition. Prior to being treated, the
crude glycerin may have a basic pH (e.g., greater than at least
about 11 or 12). After being treated, the crude glycerin may have a
lower pH (e.g., about 4.0-6.8, preferably about 5.5-6.8, and more
preferably about 5.8-6.5). The treated crude glycerin includes
glycerin (e.g., at a concentration of about 65-85%) and may include
additional components, which may include, but are not limited to,
enal compounds or enriched amounts of enal compounds (e.g.,
acrolein or "2-propenal"), reduced amounts of residual glycerides
(e.g., monoglycerides), and reduced amounts of residual volatiles
(e.g., alcohol such as methanol or ethanol).
[0010] In some embodiments, the pH of the crude glycerin is
adjusted by adding an acid to the crude glycerin. Suitable acids
include, but are not limited to, organic acids such as carboxylic
acids (e.g., acetic acid, propionic acid, butyric acid, valeric
acid, or mixtures thereof), inorganic acids (e.g., phosphoric acid,
sulfuric acid, or mixtures thereof), or mixtures of organic acids
and inorganic acids. Suitable acids may include
polyhydroxycarboxylic acids (e.g., citric acid). In some
embodiments, the acid is a mixture an organic acid and an inorganic
acid, such as a mixture of propionic acid and phosphoric acid
(preferably at a ratio of about (3-1):1 or at a ratio of about
2:1).
[0011] The disclosed compositions may be prepared from crude
glycerin that includes, as an additional component, an enal
compound such as acrolein (i.e., 2-propenal). The crude glycerin
may be treated in order to increase the amount of enal compounds
present in the crude glycerin. For example, in some embodiments,
the crude glycerin may be treated by heating the crude glycerin to
about 200-300.degree. C. In other embodiments, the crude glycerin
may be treated by reacting the crude glycerin with sodium bisulfate
or potassium bisulfate. In some embodiments, the disclosed
compositions may include at least about 1% acrolein (preferably at
least about 2%, 3%, 4%, or 5% acrolein).
[0012] In some embodiments, the crude glycerin optionally is
treated by performing one or more steps such as heating, refluxing,
condensing, and distilling. For example, the pH of the crude
glycerin may be adjusted to about 4.0-6.8 (preferably about
5.5-6.8, and more preferably about 5.8-6.5) to obtain a neutralized
composition; optionally, any solid precipitate formed in the
neutralized composition may be removed; and optionally, the
neutralized composition may be heated to a temperature greater than
about 80.degree. C. (preferably greater than about 85.degree. C. or
greater than about 90.degree. C.) under vacuum. A volatile
distillate fraction may be removed from the composition thusly
heated leaving a retained fraction. In further embodiments, the
retained fraction, may be heated, refluxed, condensed, or
distilled, for example, by heating the retained fraction to a
temperature of about 200-300.degree. C. (preferably about
220-250.degree. C.) for at least about 30 minutes (preferably for
about 60-90 minutes), thereby obtaining a refluxed glycerin
composition. The refluxed glycerin composition optionally may be
heated to temperatures ranging from about 40-250.degree. C. and one
or more distillates may be collected. In some embodiments, a
distillate is collected where the distillate has a boiling point
range of about 50-100.degree. C. The refluxed glycerin and
collected distillates may have an enriched concentration of enal
compounds (e.g., at least about 1%, 2%, 3%, 4%, 5%, 10%, or 15%
acrolein).
[0013] The disclosed composition may be utilized as
soil-amendments. In some embodiments, the composition includes a
treated crude glycerin composition and further may include a
nitrogen source. In some embodiments, the disclosed compositions
include a treated crude glycerin composition and nitrogen source
and have a molar ratio of total carbon to total nitrogen (C:N) of
about (22.4-5.6):1, and preferably about (16.8-11.2):1. Nitrogen
sources may include organic nitrogen sources, inorganic nitrogen
sources, or a mixture thereof. Suitable organic nitrogen sources
may include, but are not limited to, urea, casein, and mixtures
thereof. Addition suitable sources of organic nitrogen may include,
but are not limited to, manure (e.g., dairy manure, cage manure
including egg layers' manure, or mixtures thereof), hay (e.g.,
legume hay, grass hay, or mixtures thereof), and meal (e.g.,
alfalfa meal, soybean meal, blood meal, cottonseed meal, crab meal,
fish meal, feather meal, or mixtures thereof). Suitable inorganic
nitrogen sources may include, but are not limited to, ammonium
salts (e.g., ammonium sulfate), nitrite salts, nitrate salts (e.g.,
potassium nitrate or ammonium nitrate), and mixtures thereof
Preferably, the nitrogen source may be readily assimilated by
plants when the disclosed compositions are utilized as
soil-amendments. The nitrogen source may be added to the treated
glycerin composition as a solid or as a solution. In further
embodiments, the disclosed compositions do not include a nitrogen
source and may be added to soil as an amendment in order to achieve
in the amended soil a molar ratio of total carbon to total nitrogen
(C:N) of about (22.4-5.6):1, and preferably about (16.8-11.2):1,
where the soil, prior to amendment, includes a nitrogen source.
[0014] The disclosed compositions typically include a treated crude
glycerin composition and further may include additional components
that are suitable as soil-amendments. For example the disclosed
compositions may include additional components such as pesticides
(e.g., nematocides, insecticides, fungicides, and herbicides),
fertilizers, or both. In some embodiments, the disclosed
compositions include a treated crude glycerin composition and
further include a sulfur compound.
[0015] Also disclosed are methods for preparing the disclosed
compositions. In some embodiments, the disclosed methods include
methods for preparing a soil-amendment composition for controlling
soil-bourne pests, weeds, or both, and may include the steps of (i)
adjusting the pH of a crude glycerin composition to about 4.0-6.8
(preferably 5.5-6.8, and more preferably 5.8-6.5) to obtain a
neutralized composition, where the crude glycerin composition is
obtained as a by-product of a reaction mixture for producing
biodiesel fuel; and (ii) removing an insoluble precipitate from the
neutralized composition; thereby obtaining the treated crude
glycerin composition. The treated crude glycerin composition may be
utilized as a soil-amendment composition or optionally further may
be treated (e.g., subjected to heating, refluxing, condensation, or
distillation) or further may be combined with additional
ingredients (e.g., a nitrogen source). In some embodiments, the
crude glycerin composition is further treated by: (iii) performing
one or more steps such as heating, refluxing, condensing, and
distilling the neutralized composition; and optionally (iv)
removing or collecting a volatile distillate fraction; thereby
obtaining the treated crude glycerin composition suitable for use
as a soil-amendment composition. In further embodiments, the
treated crude glycerin composition further is combined with an
effective amount of nitrogen source; wherein the composition has a
molar ratio of total carbon to total nitrogen (C:N) of about
(22.4-5.6):1, and preferably of about (16.8-11.2):1.
[0016] Also disclosed are methods for controlling soil-bourne
pests, weeds, or both. The methods may include applying the
disclosed compositions as a liquid soil-amendment composition at an
application rate of at least about 1 ml/kg soil (optionally at an
application rate of at least about 2 ml/kg soil, 3 ml/kg soil, or 4
ml/kg soil). The selected application rates may achieve an
effective concentration of acrolein in soil for controlling pest,
weeds, or both (e.g., at least about 25 mg acrolein/kg soil, 50 mg
acrolein/kg soil, 100 mg acrolein/kg soil, 200 mg acrolein/kg soil,
or 300 mg acrolein/kg soil). The soil-amendment composition may
comprise an effective amount of a treated crude glycerin
composition, where the crude glycerin composition is obtained as a
by-product of a reaction mixture for producing biodiesel fuel and
the crude glycerin composition is treated by: (i) adjusting the pH
of the crude glycerin composition to about 4.0-6.8 (preferably
5.5-6.8, and more preferably 5.8-6.5) to obtain a neutralized
composition; and (ii) removing an insoluble precipitate from the
neutralized composition; thereby obtaining the treated crude
glycerin composition. Optionally, the crude glycerin composition
may be further treated by (iii) performing one or more steps such
as heating, refluxing, condensing, and distilling the neutralized
composition; and optionally (iv) removing or collecting a volatile
distillate fraction; thereby obtaining the treated crude glycerin
composition. Optionally, the soil-amendment further comprises an
effective amount of an organic nitrogen source; where the
soil-amendment composition has a molar ratio of total carbon to
total nitrogen (C:N) of about (22.4-5.6):1, and preferably of about
(16.8-11.2):1.
BRIEF DESCRIPTION OF THE FIGURES
[0017] FIG. 1. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without added urea (150 mg/kg soil) on nematode population
(Rotylenchulus reniformis/100 ml soil) was assessed.
[0018] FIG. 2. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without urea (150 mg/kg soil) on nematode population
(Microbivorous/100 ml soil) was assessed.
[0019] FIG. 3. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without urea (150 mg/kg soil) on nematode population
(Dorylaimida/100 ml soil) was assessed.
[0020] FIG. 4. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
130-245.degree. C., 245-250.degree. C., 250.degree. C.,
250-255.degree. C., 255-260.degree. C., and 260-275.degree. C.) at
various application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg
soil) on nematode population (Rotylenchulus reniformis/100 ml soil)
was assessed.
[0021] FIG. 5. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
130-245.degree. C., 245-250.degree. C., 250.degree. C.,
250-255.degree. C., 255-260.degree. C., and 260-275.degree. C.) at
various application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg
soil) on nematode population (Microbivorous/100 ml soil) was
assessed.
[0022] FIG. 6. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
130-245.degree. C., 245-250.degree. C., 250.degree. C.,
250-255.degree. C., 255-260.degree. C., and 260-275.degree. C.) at
various application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg
soil) on nematode population (Dorylaimida/100 ml soil) was
assessed.
[0023] FIG. 7. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
73.degree. C., 73-76.degree. C., 76-86.degree. C., 86-96.degree.
C., 96-130.degree. C., and 245-250.degree. C.) at various
application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) on
nematode population (Rotylenchulus reniformis/100 ml soil) was
assessed.
[0024] FIG. 8. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
73.degree. C., 73-76.degree. C., 76-86.degree. C., 86-96.degree.
C., 96-130.degree. C., and 245-250.degree. C.) at various
application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) on
nematode population (Microbivorous/100 ml soil) was assessed.
[0025] FIG. 9. The effect of distilled fractions of neutralized
bioglycerin compositions (see Examples 1-3, fractions collected at
73.degree. C., 73-76.degree. C., 76-86.degree. C., 86-96.degree.
C., 96-130.degree. C., and 245-250.degree. C.) at various
application rates (0 ml/kg soil, 1 ml/kg soil, or 3 ml/kg soil) on
nematode population (Dorylaimida/100 ml soil) was assessed.
[0026] FIG. 10. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without added urea (150 mg/kg soil) on nematode population
(Rotylenchulus reniformis/100 ml soil) was assessed.
[0027] FIG. 11. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without added urea (150 mg/kg soil) on cotton plant
emergence (cotton plant per pot) was assessed. The presence of urea
was observed to result in an increase in the number of cotton
plants per pot.
[0028] FIG. 12. The effect of a neutralized bioglycerin composition
(see Example 1) at various application rates (0 ml/kg soil, 1 ml/kg
soil, 2 ml/kg soil, 3 ml/kg soil, 4 ml/kg soil, or 5 ml/kg soil)
with or without added urea (150 mg/kg soil) on cotton plant shoot
weight (grams) was assessed. The presence of urea was observed to
result in an increase in the weight of fresh shoots.
DETAILED DESCRIPTION
[0029] The present invention is described herein using several
definitions, as set forth below and throughout the application.
[0030] Unless otherwise specified, the terms "a" or "an" mean "one
or more."
[0031] As used herein, "about" and "substantially" will be
understood by persons of ordinary skill in the art and will vary to
some extent on the context in which they are used. If there are
uses of the term which are not clear to persons of ordinary skill
in the art given the context in which it is used, "about" will mean
up to plus or minus 10% of the particular term and "substantially"
will mean more than plus or minus 10% of the particular term.
[0032] As used herein, "crude glycerin," "biodiesel glycerin,"
"biodiesel fuel glycerin," "BDF glycerin," or "bioglycerin" refer
to a glycerin composition that is obtained as a by-product of a
reaction for producing biodiesel fuel (BDF), and which may be
further treated or left untreated. The reaction for producing BDF
may include a transesterification reaction or alcoholysis reaction
that occurs in a basic reaction mixture (e.g., having a pH greater
than about 11) comprising triglycerides (e.g., which are present in
animal or vegetable fats or oils) and alcohol (e.g., methanol or
ethanol). The reaction mixture may produce fatty acid alkyl esters
(e.g., fatty acid methyl esters) and glycerin. As used herein,
"glycerin," "glycerine," or "glycerol" refers to the compound
1,2,3, propanetriol.
[0033] The disclosed compositions may include liquid compositions.
Unless indicated as otherwise, percentage concentrations refer to
percentage on a volume/volume basis.
[0034] The disclosed compounds may be utilized as soil-amendments.
Glycerin is not only a good carbon source for some microorganisms
in soil but BDFs glycerin also contain acrolein, potentially a
desirable component in development of glycerin-based organic
amendments. The heating of glycerin at to high temperatures results
in dehydration, re-arrangement and formation of enal compounds such
as acrolein (i.e., "2-propenal") (Merck Index. 1989. 11.sup.th
Edition. Merck & Co., Inc. Rahwayt, J. J. U.S.A.; and Whitmore,
F. C. 1951. Orgnic Chemistry. Vol. 1. Dover Publications, Inc. New
York.; incorporated by reference herein in their entireties).
Acrolein is a toxic compound registered for use in control of
aquatic weeds (Meister Pro. 2006. Crop Protection Handbook. Moister
Media, Willoughby, Ohio, incorporated by reference herein in its
entirety). Research at Auburn University has demonstrated that
acrolein has fungicidal and nematocidal activities in greenhouse
and field experiments (Belcher, J. L., R. H. Walker, R.
Rodriguez-Kabana, E. Guertal, and L. E. Simmons, 2005, Proceedings
Annual International Research Conference on Methyl Bromide
Alternatives and Emissions Reductions, Oct. 31-Nov. 3, 2004, San
Diego, Calif., Paper No.24; Belcher, J. L., R. H. Walker, and K
Rodriguez-Kabana, 2004, Proceedings Annual International Research
Conference on Methyl Bromide Alternatives and Emissions Reductions,
Oct. 31-Nov. 3, 2004, Orlando, Fla., Paper No. 23; Rodriguez-Kabana
et al., U.S. patent application Ser. No. 11/260,771, filed Oct. 27,
2005; Rodriguez-Kabana, R, L. J.. Simmons, R. H. Walker, E. A.
Guertal, & D. H. Teem, 2004, Proceedings Annual International
Research Conference on Methyl Bromide Alternatives and Emissions
Reductions, Oct. 31-Nov. 3, 2004, Orlando, Fla. Paper No. 22;
Rodriguez-Kabana, R., E. A. Guertal, R. H. Walker, and D. H. Teem,
2003, Proceedings Annual International Research Conference on
Methyl Bromide Alternatives and Emissions Reductions, Nov. 3-6,
2003, San Diego, Calif., Pages 51-1 to 51-7; incorporated herein by
reference in their entireties).
[0035] The disclosed compositions may include enal compounds. Enal
compounds may include dehydration products of glycerol compounds.
As used herein, enal compounds include 2-propenal (i.e., acrolein)
and polymers thereof. In some embodiments, the disclosed
compositions may include at least about 1%, 2%, 3%, 4%, 5%, 10%, or
15% 2-propenal and polymers thereof.
[0036] The disclosed compositions may include treated glycerin
compositions and may be used as soil-amendments that exhibit
fertilizing activity. For example, the disclosed compositions may
include one or more of assimilable potassium, phosphorus, and
nitrogen. In some embodiments, the treated glycerin composition is
prepared from a crude glycerin composition that is obtained from a
transesterification reaction in which a potassium salt is used as a
catalyst or a basifying agent (e.g., KOH or KOCH.sub.3). In further
embodiments, the crude glycerin composition is treated with a
phosphorus-containing acid (e.g., phosphoric acid or phosphorous
acid). In even further embodiments, a nitrogen source may be added
to the treated glycerin composition to provide a soil-amendment
composition having a suitable C:N ratio.
[0037] Incorporation into soil of organic matter with the
appropriate C:N ratio is one of the best methods to suppress plant
parasitic nematodes and other soil-borne pests. Stimulation of
microbial activities in soil following incorporation of organic
amendments has been repeatedly demonstrated to results in control
of plant parasitic nematodes, a number of phytopathogenic fungi and
even some insects and weeds. (Rodriguez-Kabana, R, and M. H. Pope,
Nematropica 11: 175-186 (1986); Rodriguez-Kabana, R., G.
Morgan-Jones, and T. Chet. 1987. Plant and Soil 100: 237-247;
Stirling, G. K 1991. Biological control of plant parasitic
nematodes: progress, problem and prospects. Wallingford, Oxon, UK,
CAB International, pp. 282; incorporated herein by reference in
their entireties). Considerable research has been directed to the
preparation of organic amendments based on agricultural wastes and
other by-products of human activities, e.g., chicken and other
manures, sewage and other urban ordures, in order to dispose
ofthese materials in an environmentally acceptable manner
(Stirling, 1991). In some embodiments, the disclosed compositions
include a nitrogen source which may be an organic nitrogen source
or an inorganic nitrogen source. Preferably, the nitrogen source is
soluble in glycerin. The disclosed compositions may have a suitable
C:N ratio (e.g., a C:N ration that about (22.4-5.6):1 or about
(16.8-11.2):1).
[0038] As used herein, the phrase "effective amount" or "effective
rate" shall mean that amount or rate that provides the specific
response for which the composition is applied in a significant
number of applications. The disclosed compositions may include an
effective amount of the treated glycerin compositions to achieve a
pesticidal effect (e.g., a nematocidal, a fungicidal, an
herbicidal, or insecticidal effect) when applied at a given
application rate. In some embodiments, the treated glycerin
compositions may include enal compounds (e.g., 2-propenal).
Effective amounts of enal compounds (e.g., 2-propenal) and
effective application rates for compositions that comprise enal
compounds for controlling pests and weeds are disclosed in U.S.
patent application Ser. No. 11/260,771, which is incorporated
herein by reference in its entirety. In some embodiments, the
disclosed compositions include 2-propenal and are applied to soil
as an amendment at an application rate that achieves an effective
concentration of 2-propenal of at least about 25 mg/kg soil (or at
least about 50 mg/kg soil, 100 mg/kg soil, 200 mg/kg soil, or 300
mg/kg soil).
[0039] The disclosed compositions may be utilized to control one or
more pests (e.g. parasitic nematodes, fungi, and weeds). In some
embodiments, the disclosed compositions are applied to soil at a
given rate (e.g., about 1 ml/kg soil, about 2 ml/kg soil, about 3
ml/kg soil, or about 4 ml/kg soil) and reduce the pest population
in the soil (e.g., parasitic nematodes as measured by number of
pests/mls soil) by at least about 50% (or at least about 60%, 70%,
80%, or 90%). In further embodiments, the disclosed compositions do
not significantly reduce the population of beneficial nematodes
present in the soil (e.g., microbivores), where the disclosed
composition are applied to soil at a given rate (e.g., about 1
ml/kg soil, about 2 ml/kg soil, about 3 ml/kg soil, or about 4
ml/kg soil) and do not reduce the beneficial nematode population in
the soil by more than about 50% (or no more than about 40%, 30%,
20%, or 10%).
Illustrative Embodiments
[0040] The following list of embodiments is illustrative and is not
intended to limit the scope of the claimed subject matter.
Embodiment 1
[0041] A soil-amendment composition for controlling soil-bourne
pests, the composition comprising: (a) an effective amount of a
treated crude glycerin composition, wherein the crude glycerin
composition is obtained as a by-product of a reaction mixture for
producing biodiesel fuel and the crude glycerin composition is
treated by: (i) adjusting the pH of the crude glycerin composition
to about 4.0-6.8 to obtain a neutralized composition; and (ii)
removing an insoluble precipitate from the neutralized composition;
thereby obtaining the treated crude glycerin composition; and (b)
an effective amount of a nitrogen source; wherein the composition
has a molar ratio of total carbon to total nitrogen (C:N) of about
(22.4-5.6):1, preferably about (16.8-11.2):1.
Embodiment 2
[0042] The soil-amendment composition of embodiment 1, wherein the
crude glycerin composition is further treated by: (iii) heating the
neutralized composition; and (iv) removing a volatile distillate
fraction from the neutralized composition; thereby obtaining the
treated crude glycerin composition.
Embodiment 3
[0043] The soil-amendment composition of embodiment 2, wherein the
crude glycerin composition is further treated by: (v) refluxing the
neutralized composition; and (vi) distilling and collecting a
volatile distillate fraction; thereby obtaining the treated crude
glycerin composition.
Embodiment 4
[0044] The composition of any of embodiments 1-3, wherein the
soil-bourne pests are parasitic nematodes.
Embodiment 5
[0045] The composition of any of embodiments 1-4, wherein the
composition is effective for reducing parasitic nematodes by at
least about 50% when applied at an application rate of about 1
ml/kg soil.
Embodiment 6
[0046] The composition of any of embodiments 1-5, wherein the
composition does not reduce microbivorous nematodes by more than
about 50% when applied at an application rate of about 1 ml/kg
soil.
Embodiment 7
[0047] The composition of any of embodiments 1-6, wherein the
reaction mixture for producing biodiesel fuel comprises: (a) animal
or vegetable fats or oils, or a mixture thereof; (b) a base,
wherein the reaction mixture has a pH of at least about 11; and (c)
an alcohol.
Embodiment 8
[0048] The composition of embodiment 4, wherein the base is
selected from the group consisting of NaOH, KOH, NaOCH.sub.3 and
KOCH.sub.3.
Embodiment 9
[0049] The composition of embodiment 4, wherein the alcohol is
methanol or ethanol.
Embodiment 10
[0050] The composition of any of embodiments 1-9, wherein prior to
being treated the crude glycerin composition comprises: (a) about
65-85% glycerin; (b) acrolein; (c) monoglycerides; and (d) alcohol;
and the crude glycerin composition has a pH of greater than about
11.
Embodiment 11
[0051] The composition of any of embodiments 1-10, wherein the
treated crude glycerin composition comprises: (a) about 65-85%
glycerin; and (b) acrolein; and (c) no more than about 10%
monoglycerides (preferably no more than about 8%, 6%, 4%, or 2%
monoglycerides).
Embodiment 12
[0052] The composition of embodiment 2, wherein the treated crude
glycerin composition comprises: (a) about 65-85% glycerin; and (b)
acrolein; and (c) no more than about 15% alcohol (preferably no
more than 10% or 5% alcohol).
Embodiment 13
[0053] The composition of embodiment 3, wherein the treated crude
glycerin composition comprises: (a) about 65-85% glycerin; and (b)
at least about 5% acrolein (preferably at least about 10% or 15%
acrolein).
Embodiment 14
[0054] The composition of any of embodiments 1-13, wherein
adjusting the pH of the crude glycerin composition to about 4.0-6.8
comprises adding an acid to the composition.
Embodiment 15
[0055] The composition of embodiment 14, wherein the acid is an
organic acid.
Embodiment 16
[0056] The composition of embodiment 14, wherein the organic acid
is a carboxylic acid.
Embodiment 17
[0057] The composition of embodiment 16, wherein the carboxylic
acid is acetic acid, propionic acid, butyric acid, or a mixture
thereof
Embodiment 18
[0058] The composition of embodiment 14, wherein the organic acid
is a polyhydroxy carboxylic acid.
Embodiment 19
[0059] The composition of embodiment 18, wherein the polyhydroxy
carboxylic acid is citric acid.
Embodiment 20
[0060] The composition of embodiment 14, wherein the acid is an
inorganic acid.
Embodiment 21
[0061] The composition of embodiment 20, wherein the inorganic acid
is phosphoric acid or sulfuric acid (preferably phosphoric
acid).
Embodiment 22
[0062] The composition of embodiment 14, wherein the acid is a
mixture of an organic acid and an inorganic acid.
Embodiment 23
[0063] The composition of embodiment 2, wherein heating comprises
heating the neutralized composition to a temperature of at least
about 80.degree. C. (preferably at least about 80.degree. C. or
90.degree. C.) under vacuum, preferably at least about 500 mm Hg
(19 inch Hg), 600 mm Hg (23 inch Hg), or 700 mm Hg (27 inch
Hg).
Embodiment 24
[0064] The composition of embodiment 3, wherein refluxing comprises
heating the neutralized composition to a temperature of about
200-350.degree. C. (preferably at a temperature of about
200-300.degree. C. or about 220-250.degree. C.) through a
condenser; and distilling comprises heating the neutralized
composition and collecting distillates through a temperature range
of about 40-250.degree. C.
Embodiment 25
[0065] The composition of any of embodiments 1-24, wherein the
nitrogen source is an organic nitrogen source (e.g., urea, casein,
or a mixture thereof).
Embodiment 26
[0066] The composition of any of embodiments 1-25, wherein the
crude glycerin composition further is treated by reacting the
composition with sodium bisulfate or potassium bisulfate.
Embodiment 27
[0067] The composition of any of embodiments 1-26, further
comprising sulfur.
Embodiment 28
[0068] A method for preparing a soil-amendment composition for
controlling soil-bourne pests, the method comprising combining: (a)
an effective amount of a treated crude glycerin composition,
wherein the crude glycerin composition is obtained as a by-product
of a reaction mixture for producing biodiesel fuel and the crude
glycerin composition is treated by: (i) adjusting the pH of the
crude glycerin composition to about 4.0-6.8 to obtain a neutralized
composition; and (ii) removing an insoluble precipitate from the
neutralized composition; thereby obtaining the treated crude
glycerin composition; and (b) an effective amount of an organic
nitrogen source; wherein the composition has a molar ratio of total
carbon to total nitrogen (C:N) of about (22.4-5.6):1, preferably
about (16.8-11.2):1.
Embodiment 29
[0069] The method of embodiment 28, wherein the crude glycerin
composition is further treated by: (iii) heating the neutralized
composition; and (iv) removing a volatile distillate fraction from
the neutralized composition; thereby obtaining the treated crude
glycerin composition.
Embodiment 30
[0070] The method of embodiment 29, wherein the crude glycerin
composition is further treated by: (v) refluxing the neutralized
composition; and (vi) distilling and collecting a volatile
distillate fraction; thereby obtaining the treated crude glycerin
composition.
Embodiment 31
[0071] A method for preparing a soil-amendment composition for
controlling soil-bourne pests, the method comprising: (a) adjusting
the pH of a crude glycerin composition to about 4.0-6.8 to obtain a
neutralized composition; wherein the crude glycerin composition is
obtained as a by-product of a reaction mixture for producing
biodiesel fuel; (b) removing an insoluble precipitate from the
neutralized composition, thereby obtaining a treated crude glycerin
composition; and (c) combining an effective amount of the treated
crude glycerin composition and an effective amount of an organic
nitrogen source such that the composition has a molar ratio of
total carbon to total nitrogen (C:N) of about (22.4-5.6):1,
preferably about (16.8-11.2):1.
Embodiment 32
[0072] The method of embodiment 31, further comprising heating the
neutralized composition; and removing a volatile distillate
fraction from the neutralized composition; thereby obtaining the
treated crude glycerin composition.
Embodiment 33
[0073] The method of embodiment 32, further comprising refluxing
the neutralized composition; and distilling and collecting a
volatile distillate fraction; thereby obtaining the treated crude
glycerin composition.
Embodiment 34
[0074] A method for controlling soil-bourne pests comprising
applying a liquid soil-amendment composition at an application rate
of at least about 1 ml/kg soil, the soil-amendment composition
comprising: (a) an effective amount of a treated crude glycerin
composition, wherein the crude glycerin composition is obtained as
a by-product of a reaction mixture for producing biodiesel fuel and
the crude glycerin composition is treated by: (i) adjusting the pH
of the crude glycerin composition to about 4.0-6.8 to obtain a
neutralized composition; and (ii) removing an insoluble precipitate
from the neutralized composition; thereby obtaining the treated
crude glycerin composition; and (b) an effective amount of an
organic nitrogen source; wherein the composition has a molar ratio
of total carbon to total nitrogen (C:N) of about (22.4-5.6):1,
preferably about (16.8-11.2):1.
Embodiment 35
[0075] The method of embodiment 34, wherein the crude glycerin
composition is further treated by: (iii) heating the neutralized
composition; and (iv) removing a volatile distillate fraction from
the neutralized composition; thereby obtaining the treated crude
glycerin composition.
Embodiment 36
[0076] The method of embodiment 35, wherein the crude glycerin
composition is further treated by: (v) refluxing the neutralized
composition; and (vi) distilling and collecting a volatile
distillate fraction; thereby obtaining the treated crude glycerin
composition.
EXAMPLES
[0077] The following examples are illustrative and are not intended
to limit the scope of the claimed subject matter.
[0078] Example 1--Neutralization of Crude Glycerin Product (CGP)
from Biodiesel Production
[0079] A crude glycerin product (CGP) is produced from a
transesterification reaction between sodium (or potassium)
methylate and vegetable or animal oils or fats (i.e., glycerin
esters of fatty acids). The transesterification reaction produces
biodiesel (i.e., methyl esters of the fatty acids) and about 12-14%
CGP. The pH of CGP is typically in the range of 11.5-12.5 and most
commonly 12.00. Use of the CGP in agriculture requires lowering of
pH to within an acceptable level for addition to soil (e.g., a pH
of about 5.8-6.5).
Procedure
[0080] CGP was obtained from Alabama Biodiesel Corporation,
Moundville, AL, producers of biodiesel from food grade soybean oil.
In the typical laboratory procedure, 32 mls of propionic acid are
added slowly in 5-8 ml aliquots while stirring into filtered and
clear 500 mls CGP. A final pH of 6.5 is attained. During the
neutralization process, when the pH nears about 8.00, a clouding is
observed due to precipitation of free long-chained fatty acids.
These acids are either present in the vegetable oil or may be
formed during the trans-methylation reaction--the acids react with
Na.sup.+ or K.sup.+ cations to form fatty acid salts (i.e., soaps).
On standing overnight (10-14 hrs) at room temperature
(20-23.degree. C.), the soaps float to the surface of the
neutralized mixture and are separated from the clear underlying
neutralized bioglycerin (NBG). The amount of soap collected amounts
to some 10-15% of the final volume when propionic acid is used.
[0081] Other acids that can be used and the amount needed for
neutralization (parenthesis) of 500 mls CGP to pH 6.5 are: glacial
acetic (17 mls); butyric acid (30 mls); valeric acid (38 mls);
citric acid (19 gms); 96% sulfuric acid (7 mls); 85% phosphoric
acid (14 mls). The amount of soap formed varies considerably among
the acids. The preferred organic acids are acetic acid and
propionic acid. The preferred inorganic acid is phosphoric acid. A
2:1 mixture of (propionic acid):(phosphoric acid) is preferred when
NBG is to be used as an organic amendment to soil--phosphoric acid
providing the necessary phosphorus for microbial metabolism and
plant growth.
[0082] NBG thus prepared can be added directly to soil for control
of nematodes and other soil-borne pests. (See Example 4 and FIGS.
1-3 and 10-12.) It typically contains by volume: glycerin
(.about.73%), recoverable volatiles (.about.23%), and unrecoverable
volatiles (4%). The amount of glycerin and volatiles will vary with
the type of oil or fat used to make biodiesel and the acid used to
neutralize CGP.
Example 2--Removal of Volatile Components from Neutralized
Bioglycerin (NBG)
[0083] Neutralized bioglycerin (NBG) contains significant amounts
of volatile compounds that preferably are removed prior to thermal
reduction of glycerin (i.e., refluxing) and formation of acrolein
(i.e., 2-propenal) and related enal compounds with pesticidal
properties. (See pending U.S. application Ser. No. 11/260,771,
which content is incorporated herein by reference in its
entirety).
Procedure
[0084] 500 mls NBG are placed in a 2L round bottom flask which is
connected to a rotary evaporator (Evapotec, Haaken Buehler) and
lowered into a water bath set with water at 90.degree. C. The flask
is then rotated at 200 rpm and vacuum is applied at -700 mm Hg (-27
inch Hg) while cool water (5.degree. C.) is run through the
condenser coils. Volatiles are collected in a 1 L round bottom
flask attached to bottom of the condenser section of the apparatus.
The operation is stopped after approx. 30 min when 95-98% of
volatiles are collected. The glycerin in the 2 L flask is now
essentially free of low boiling compounds and is ready for
refluxing and thermal reduction and distillation. Volatiles
collected consist of methanol, and residual propionic acid, esters,
and turpentine-like smelling compounds of unknown identity.
Example 3--Refluxing and Distillation of Neutralized Bioglycerin
(NBG)
[0085] Condensation and reduction of glycerin occurs in nature
during the burning of fats and oils. The process results in
formation of acrolein (i.e., 2-propenal) and polymers thereof.
These enal compounds because of their conjugate double bond with
aldehyde group are very reactive and have a strong broad-spectrum
of pesticidal activities (weeds, nematodes, fungi . . . etc.). The
reduction and condensation of glycerin can be catalyzed by strong
acids (especially H.sub.2SO.sub.4 or NaHSO.sub.4). Acid, however,
may not be required if the glycerin is heated at temperatures of
about 200-300.degree. C. In this manner, it is possible to enrich
"stripped NBG" of its acrolein content and increase its pesticidal
properties. "Stripped NBG" refers to NBG having reduced volatiles
after having performed the method described in Example 2.
Procedure
[0086] Step 1. 500 mls of stripped NBG is placed in a 2 L
round-bottom flask in a Barnstead Magnistir variable heater and
heated to about 110.degree. C. for about 15-20 min while stirring
vigorously. This step helps reduce or eliminate any residual water.
A Liebig type condenser is then fitted upright into the neck of the
2L flask, cool water (about 5-10.degree. C.) is run through the
condenser and the temperature is gradually increased to about
220-250.degree. C.; the liquid thus being refluxed is kept stirred
vigorously for about 60-90 min while manipulating the temperature
to avoid foaming. At the end of the refluxing period, the
temperature is slowly reduced to less than about 40.degree. C. and
the condenser is carefully removed. A brown to dark liquid with a
lachrymatory acrid vapor (producing tears) should be present in the
flask.
[0087] Step 2. The 2 L flask with reduced glycerin from step 1 and
still in the heater, is now connected to a simple column
distillation apparatus. The temperature is gradually increased and
distillates are collected through a temperature [T] range of about
40.ltoreq.T<250.degree. C. The distilled fraction can be added
directly to soil for control of nematodes and other soil-borne
pests. (See Example 4 and FIGS. 4-9).
Comments
[0088] Removal of soaps after neutralization of CGP may be
essential to avoid excessive foaming. The pH of stripped NBG
preferably should be on the acid side, preferably in the range of
about 4.5-5.5. If necessary this can be attained by adjusting the
pH with H.sub.3PO.sub.4. The chemical composition of the various
distillates is quite varied and at this point not completely
elucidated. They all contain some acrolein with most of that
compound distilling over in the range of about 50-100.degree. C.
Higher boiling distillates are presumed to be polymers of the
compound as well as other chemically reduced unknown entities.
Example 4--Use of Treated Crude Glycerin Products as Soil
Amendments
Objective 1
[0089] Factorial greenhouse experiments will be established to
determine the efficacy of glycerin containing increasing
concentrations of acrolein for control of the reniform nematode
(Rotylenchulus reniformis), and of common damping off and seedling
disease fungi (Rhizoctonia solani, and species of Pythium and
Fusarium). Soils for these experiments will be naturally infested
with the pathogens and obtained from fields known to be infected
with nematodes or fungi. In each experiment, the moist soil (60%
field capacity) will be apportioned in 1 kg amounts contained in 1
L cylindrical PVC pots with 1 mm mesh non-metal screen bottoms.
Glycerin-acrolein mixtures will be delivered by drenching in 100
mls aqueous solutions/pot (equivalent to 1 acre inch water).
Immediately after treatment, the pots will be covered with
polyethylene bags (2 mil) and placed on a greenhouse bench. The
bags will be removed after 2 wks and soil samples will be taken for
nematological analyses by the salad bowl incubation technique
(Rodriguez-Kabana & Pope, Nematropica 11:175-186 (1987)).
"Hutchenson" soybean (reniform nematode susceptible) will be
planted (5 seed/pot) and allowed to grow for 6 weeks when the
plants will be removed and data collected on: number of surviving
plants, phytotoxicity, and plant growth parameters (shoot height
and weights of shoots and roots), and nematode populations in soil
and root systems (salad bowl incubation).
[0090] In experiments with fungal pathogens, 20 annual morning
glory seed (mixture of Ipomoea hederacea and I. lacunosa seed) will
be uniformly distributed and slightly pressed onto the soil surface
of each pot. The seeds will be covered with approx. 5 mm layer of
moist fine siliceous sand. The number of emerging morning glory
plants will be determined every 5-7 days for one month. Previous
studies have shown that the number of emerging plants is inversely
related to the level of damping off and seedling disease
(unpublished data). Experiments on herbicidal activity will be
performed using a sandy loam soil from a field, characterized as
not having a significant nematode or fungal disease problem. The
soil will be apportioned in 1 kg amounts and placed in 6L
polyethylene bags ("chicken bags"). Soil in each bag will be
thoroughly mixed with a weed seed mixture. The mixture consists of
5 yellow nutsedge rhizomes and the seed of (number per bag): annual
morning glory mix, i.e., Ipomoea hederacea/I lacunosa, (40); large
crabgrass, i.e., Digitaria sanguinalis, (300); sicklepod, i.e.,
Senna obtusifilia, (60); jimsonweed, i.e., Datura stramonium, (80);
yellow foxtail, i.e., Setaria glauca, (100); and redroot pigweed,
i.e., Amaranthus retroflexus, (1000). The soil with weeds will be
transferred to pots and treated as described for the experiments
with nematodes and fungi. The number and species of emerging weeds
will be recorded at weekly intervals for 6 wks after removal of the
plastic bags.
[0091] There will be 14 treatments in each experiment arranged in a
randomized complete block design with 7 replications (experimental
unit=1 pot) per treatment for a total of 98 pots. It is envisioned
that there will be a minimum of 6 experiments within this
objective.
Objective 2
[0092] The ideal C/N ratios for glycerin acrolein mixtures to
assure complete decomposition of the mixtures in soil without
phytotoxic effects to succeeding crop plants will be determined.
Glycerin and acrolein contain no nitrogen, so their decomposition
in soil will be limited by the amount of available N in soil. The
treatments may result not only in partial decomposition of
glycerin-acrolein added but also in a deficiency of available N and
"yellowing" of crop plants. Greenhouse experiments will be
conducted. to determine the optimal amount of N needed to optimize
microbial decomposition of glycerin-acrolein mixtures established
from Objective I while still retaining pesticidal activity.
Factorial experiments will be set up with treatments consisting of
mixtures of an organic N source (e.g., urea, casein) and
glycerin-acrolein solutions with the highest pesticidal activities
as determined from Objective 1. The tested nitrogen sources will
include urea and casein, which are both relatively inexpensive,
commercially available, and exhibit considerable solubility in
glycerin (Merck Index, 1989). The experiments will be set up as
described for Objective 1 to determine pesticidal activities
(including nematocidal. fungicidal, and herbicidal activities) of
the glycerin acrolein-urea (GAU) and the glycerin-urea-casein (GUC)
compositions.
Objective 3
[0093] Develop formulations suitable for field use and determine
their performance for nematode control and yield response in
microplot experiments with tomato and other common horticultural
crops. Liquid formulations of GAU and GUC suitable for application
through irrigation water will be developed based on results
obtained from Objective 2. The formulations will be tested in
microplot experiments at the Microplot Experimental Unit on the
Auburn University campus. A microplot consists of an 1 ft.sup.-2
area delimited by a 2 ft-long square terra cotta chimney flue
embedded in soil with 4 inches set above ground. The microplots are
filled with silt-loam soil known to be infested with a variety of
plant pathogenic nematodes (including Meloidogyne incognita,
Hoplolaimus galeatus, Paratrichodorus minor, and others), and fungi
(including, R. solani and species of Pythium and Fusarium).
Microplots are fitted with a drip irrigation system in which each
plot has a dripper delivering 2 gallons of water per hour.
[0094] Microplots will be treated by drenching in 1 inch-acre of
water with the appropriate glycerin formulations. Immediately after
application of the treatments, the plots will be covered with clear
polyethylene (2 mil) mulch. After 3 wks, the mulch will be removed
and soil samples for nematological analyses will be collected. Each
plot will then be planted with seedlings (2/plot). There will be a
minimum of 3 experiments, one with cherry tomatoes and the other
two with eggplant and green pepper. The plants will be irrigated
and maintained in good growing conditions following standard
recommendations for production of the crops. Each microplot
experiment will have 8 treatments with 8 replications arranged in a
randomized complete block design. There will be thus 64 plots per
experiment and crop.
[0095] Data will be collected on plant survival, phytotoxicity,
growth parameters and yield. Soil and root samples will be
collected at termination of the experiments to determine nematode
populations and to estimate damage from fungal pathogens. Yield
data will be used in preliminary economic analyses.
Example 5--Treated Crude Glycerin Combined with Organic
Nitrogen
[0096] The effect of neutralized bioglyccrin (NBG), either in the
presence or absence of organic nitrogen, was tested on the growth
of cotton plants and parasitic nematodes. Neutralized bioglycerin
(NBG) was applied at rates of 0, 1, 2, 3, 4, and 5 mls/kg soil
either with or without urea (150 mgs/Kg soil of the compound to
achieve about 70 mgs N/Kg soil). Applications were performed by
drenching the soil in aqueous solution so that the final
application volume per pot was 100 mls (which is equivalent to an
acre inch of irrigation). Each pot contained 1 Kg of soil infested
with the reniform nematode Rotylenchulus reniformis and there were
7 replications (pots)/treatment. Thus, for example, for the 1 ml
NBG application there were 14 pots, 7 of which received each water
up to 100 mls containing 1 ml NBG; the other 7 pots received each 1
ml NBG+150 mgs urea mixed in a final volume of 100 mls. The
carbon:nitrogen ratios (C/N) of the combined treatments ranged from
about 5.6 for the 1 ml NBG treatment to 28 for the 5 mls NBG
treatment. Urea alone (0 mls NBG) suppressed reniform nematode
numbers but proved phytotoxic to cotton plants where a lower number
of cotton plants per pot were observed. Applications of NBG without
urea, while detrimental to the nematode (see FIG. 10), did not
improve cotton plant survival and in fact was somewhat detrimental
to the plants (see FIGS. 11 & 12). FIGS. 11 & 12 suggest
that C:N ratios in the range of about 5.6.ltoreq.C/N.ltoreq.22.4
(i.e., 1.ltoreq.NBG.ltoreq.4 mls/Kg soil) are optimal for nematode
control and survival of cotton plants (preferably in the range of
about 11.2.ltoreq.C/N.ltoreq.16.8 (i.e., 2.ltoreq.NBG.ltoreq.3
mls/Kg soil)).
[0097] Urea is soluble in NBG up to 40% by weight so that the two
materials can be formulated together. Ideally, the pH should be
adjusted between about 4.0 and about 5.5. Buffers composed of K
salts of H.sub.3PO.sub.4 and propionic acid (or other organic
acids) may be particularly suitable because they form strong
buffers for the required pH range and contain the nutrients P and
K. Other N compounds that can be utilized in lieu of urea include,
but are not limited to, guanidines, dicyandiamide, and oxamide.
After adding water to the NBG (e.g., about 10-20%) standard
nitrates (K or NH.sub.4.sup.+) or even ammonium sulfate and the
like can be utilized for preparing fertilizer mixtures having
pesticidal properties. Alternatively, the nitrate or ammonium salts
may be added to the NBG as aqueous solutions.
Example 6--Use of Untreated Crude Biodiesel Glycerin for
Controlling or Eliminating Weeds
[0098] The efficacy of untreated crude biodiesel glycerin for
controlling or eliminating weeds was tested against crab grass,
sickle pod, and morning glory. The untreated bioglycerin was
applied to soil at rates of 5 mls/kg soil, 10 mls/kg soil, 11
mls/kg soil, 12 mls/kg soil, 13 mls/kg soil, 14 mls/kg soil, 15
mls/kg soil, 16 mls/kg soil, 17 mls/kg soil, 18 mls/kg soil, 19
mls/kg soil, and 20 mls/kg soil. After 5, 11, 19, or 39 days, the
soil was mixed with weed seed and emerging seeds were periodically
counted. Application rates of untreated bioglycerin as low as 10
mls/kg soil were found to be effective for reducing emerging weeds.
Thus, untreated crude biodiesel glycerin may be utilized as such as
a soil-amendment for controlling or eliminating weeds, or
optionally, further may be treated as disclosed herein (e.g.,
neutralized, heated, refluxed, condensed, distilled, and combined
with additional pesticidal or fertilizing agents).
[0099] All publications and patent applications cited in this
specification are herein incorporated by reference as if each
individual publication or patent application were specifically and
individually indicated to be incorporated by reference.
* * * * *