U.S. patent application number 11/705275 was filed with the patent office on 2007-08-30 for deicing and anti-icing compositions comprising renewably-based, biodegradable 1,3-propanediol.
Invention is credited to Joseph W. DeSalvo, Gyorgyi Fenyvesi, Melissa Joerger, Robert Miller, Ann Wehner.
Application Number | 20070200087 11/705275 |
Document ID | / |
Family ID | 38372098 |
Filed Date | 2007-08-30 |
United States Patent
Application |
20070200087 |
Kind Code |
A1 |
Wehner; Ann ; et
al. |
August 30, 2007 |
Deicing and anti-icing compositions comprising renewably-based,
biodegradable 1,3-propanediol
Abstract
Disclosed herein are deicing and anti-icing compositions
comprising 1,3-propanediol, wherein the 1,3-propanediol in said
deicing or anti-icing composition has a bio-based carbon content of
about 1% to 100%. In addition, it is preferred that the
1,3-propanediol be biologically-derived, and wherein upon
biodegradation, the biologically-derived 1,3-propanediol
contributes no anthropogenic CO2 emissions to the atmosphere.
Inventors: |
Wehner; Ann; (Hockessin,
DE) ; Fenyvesi; Gyorgyi; (Wilmington, DE) ;
Miller; Robert; (Wilmington, DE) ; DeSalvo; Joseph
W.; (Lafayette Hill, PA) ; Joerger; Melissa;
(Newark, DE) |
Correspondence
Address: |
MCCARTER & ENGLISH, LLP;BASIL S. KRIKELIS
CITIZENS BANK CENTER, 919 N. MARKET STREET
SUITE 1800
WILMINGTON
DE
19801
US
|
Family ID: |
38372098 |
Appl. No.: |
11/705275 |
Filed: |
February 12, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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60772471 |
Feb 10, 2006 |
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60772194 |
Feb 10, 2006 |
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60772193 |
Feb 10, 2006 |
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60772111 |
Feb 10, 2006 |
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60772120 |
Feb 10, 2006 |
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60772110 |
Feb 10, 2006 |
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60772112 |
Feb 10, 2006 |
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60846948 |
Sep 25, 2006 |
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60853920 |
Oct 24, 2006 |
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60859264 |
Nov 15, 2006 |
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60872705 |
Dec 4, 2006 |
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60880824 |
Jan 17, 2007 |
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Current U.S.
Class: |
252/70 ;
106/13 |
Current CPC
Class: |
C10M 2207/04 20130101;
A23L 29/10 20160801; A61Q 5/12 20130101; C10M 2229/0425 20130101;
A61Q 9/04 20130101; A23L 29/04 20160801; A61K 9/282 20130101; A61Q
1/02 20130101; C12P 7/18 20130101; A61K 36/355 20130101; C07C 69/78
20130101; C10M 2207/022 20130101; C10M 2215/042 20130101; C11D
3/38663 20130101; C08K 5/103 20130101; A61K 8/92 20130101; C11D
7/5022 20130101; A61K 8/375 20130101; C09G 1/08 20130101; C10N
2040/08 20130101; A01N 1/021 20130101; A23L 33/10 20160801; A23V
2002/00 20130101; A61Q 5/02 20130101; C11D 3/2044 20130101; A61Q
13/00 20130101; A61K 36/28 20130101; A61Q 11/00 20130101; C11D
7/266 20130101; A23K 20/105 20160501; A61Q 1/10 20130101; C08K
5/053 20130101; C11D 3/3418 20130101; A61K 8/345 20130101; A61Q
19/00 20130101; A23L 33/12 20160801; A23B 7/154 20130101; A61Q
17/00 20130101; A61Q 19/10 20130101; Y02W 10/37 20150501; A61Q
19/005 20130101; A61K 36/61 20130101; A23L 29/035 20160801; A61Q
15/00 20130101; C12P 7/42 20130101; A01N 3/00 20130101; A61K 47/14
20130101; C10N 2030/64 20200501; A61K 8/0208 20130101; C07C 69/44
20130101; C11D 3/2093 20130101; A23L 2/52 20130101; C10M 129/08
20130101; C10M 2207/283 20130101; C12P 7/62 20130101; A61K 2800/75
20130101; A61K 2800/10 20130101; A61Q 1/08 20130101; A61Q 19/008
20130101; C07C 69/28 20130101; A01N 25/02 20130101; A23L 3/3463
20130101; A61K 47/10 20130101; A61Q 1/14 20130101; A61Q 5/065
20130101; C02F 5/10 20130101; C10M 2215/223 20130101; C11D 3/2068
20130101; C11C 3/003 20130101; A61Q 5/00 20130101; B01D 11/0288
20130101; C08K 2201/018 20130101; C11D 1/667 20130101; A61K 9/0019
20130101; C07C 69/16 20130101; A61Q 9/02 20130101; C07C 67/08
20130101; C09D 11/16 20130101; C09D 11/38 20130101; C09K 5/10
20130101; A61K 47/44 20130101; A61K 9/06 20130101; A61K 36/185
20130101; A61K 36/738 20130101; C11D 11/0023 20130101; C09K 3/185
20130101; A61K 31/22 20130101; A61Q 5/10 20130101; A61Q 19/002
20130101; A61Q 19/04 20130101; C09D 7/63 20180101; C09K 5/20
20130101; C11D 3/2003 20130101; C11D 11/0017 20130101; A61Q 17/04
20130101; C09D 11/03 20130101; A61K 36/02 20130101; A61Q 17/005
20130101; A61Q 19/007 20130101; C10M 2209/086 20130101; A21D 2/14
20130101; C07C 69/58 20130101; C07C 69/60 20130101; C09K 3/18
20130101; C08K 5/103 20130101; C08L 67/04 20130101; C07C 67/08
20130101; C07C 69/60 20130101; C07C 67/08 20130101; C07C 69/58
20130101; C07C 67/08 20130101; C07C 69/78 20130101; C07C 67/08
20130101; C07C 69/44 20130101; C07C 67/08 20130101; C07C 69/16
20130101; C07C 67/08 20130101; C07C 69/28 20130101 |
Class at
Publication: |
252/070 ;
106/013 |
International
Class: |
C09K 3/18 20060101
C09K003/18 |
Claims
1. A deicing or anti-icing composition comprising 1,3-propanediol
and an aqueous solution, wherein said 1,3-propanediol has a
bio-based carbon content of at least 1%.
2. The deicing or anti-icing composition of claim 1 further
comprising a pH control agent.
3. The deicing or anti-icing composition of claim 1 further
comprising a surfactant.
4. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 5% biobased carbon.
5. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 10% biobased carbon.
6. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 25% biobased carbon.
7. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 50% biobased carbon.
8. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 75% biobased carbon.
9. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 90% biobased carbon.
10. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has at least 99% biobased carbon.
11. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol has 100% biobased carbon.
12. The deicing or anti-icing composition of claim 1 wherein the
1,3-propanediol is biologically-derived.
13. The deicing or anti-icing composition of claim 12 wherein the
biologically-derived 1,3-propanediol is biologically produced
through a fermentation process.
14. A deicing or anti-icing composition comprising 1,3-propanediol
and a surfactant, wherein said 1,3-propanediol has a bio-based
carbon content of at least 1%.
15. The deicing or anti-icing composition of claim 14 further
comprising an aqueous solution.
16. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 5% biobased carbon.
17. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 10% biobased carbon.
18. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 25% biobased carbon.
19. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 50% biobased carbon.
20. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 75% biobased carbon.
21. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 90% biobased carbon.
22. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has at least 99% biobased carbon.
23. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol has 100% biobased carbon.
24. The deicing or anti-icing composition of claim 14 wherein the
1,3-propanediol is biologically-derived.
25. The deicing or anti-icing composition of claim 24 wherein the
biologically-derived 1,3-propanediol is biologically produced
through a fermentation process.
26. A deicing or anti-icing composition comprising 1,3-propanediol
wherein said 1,3-propanediol has an ultraviolet absorption at 220
nm of less than about 0.200 and at 250 nm of less than about 0.075
and at 275 nm of less than about 0.075.
27. The deicing or anti-icing composition of claim 26 wherein said
1,3-propanediol has a "b" color value of less than about 0.15 and
an absorbance at 275 nm of less than about 0.050.
28. The deicing or anti-icing composition of claim 26 wherein said
1,3-propanediol has a peroxide concentration of less than about 10
ppm.
29. The deicing or anti-icing composition of claim 26 wherein said
1,3-propanediol has a concentration of total organic impurities in
said composition of less than about 400 ppm.
30. The deicing or anti-icing composition of claim 26 wherein said
1,3-propanediol has a concentration of total organic impurities of
less than about 300 ppm.
31. The deicing or anti-icing composition of claim 26 wherein said
1,3-propanediol has a concentration of total organic impurities of
less than about 150 ppm.
32. A deicing or anti-icing composition comprising 1,3-propanediol
wherein said 1,3-propanediol has a concentration of total organic
impurities of less than about 400 ppm.
33. The deicing or anti-icing composition claim 32 wherein said
1,3-propanediol has a concentration of total organic impurities of
less than about 300 ppm.
34. The deicing or anti-icing composition claim 32 wherein said
1,3-propanediol has a concentration of total organic impurities of
less than about 150 ppm.
35. The deicing or anti-icing composition claim 32 wherein said
1,3-propanediol has a concentration of peroxides of less than about
10 ppm.
36. The deicing or anti-icing composition claim 32 wherein said
1,3-propanediol has a concentration of carbonyl groups of less than
about 10 ppm.
37. A deicing or anti-icing composition comprising 1,3-propanediol,
wherein the 1,3-propanediol in said composition has an
anthropogenic CO.sub.2 emission profile of zero upon
biodegradation.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of U.S.
Provisional Application Ser. No. 60/772,471, filed Feb. 10, 2006;
U.S. Provisional Application No. 60/772,194, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,193, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,111, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,120, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,110, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/772,112, filed Feb. 10, 2006,
U.S. Provisional Application No. 60/846,948, filed Sep. 25, 2006,
U.S. Provisional Application No. 60/853,920, filed Oct. 24, 2006,
U.S. Provisional Application No. 60/859,264, filed Nov. 15, 2006,
U.S. Provisional Application No. 60/872,705, filed Dec. 4, 2006 and
U.S. Provisional Application No. 60/880,824, filed Jan. 17, 2007,
the disclosures of which are expressly incorporated herein by
reference in their entireties.
FIELD OF THE INVENTION
[0002] Disclosed herein are deicing and anti-icing compositions
comprising 1,3-propanediol wherein the 1,3-propanediol in said
deicing and anti-icing composition has a bio-based carbon content
of about 1% to 100%. In addition, it is preferred that the
1,3-propanediol be biologically-derived, and wherein upon
biodegradation, the biologically-derived 1,3-propanediol
contributes no anthropogenic CO.sub.2 emissions to the
atmosphere.
BACKGROUND OF THE INVENTION
[0003] Consumers of deicing and anti-icing compositions consider
many factors in selecting products for use. Recently certain
factors have been a focus of and have driven scientific study and
product development. These driving factors include, product safety,
environmental impact, the extent to which the components are
natural, and the aesthetic quality of the overall product.
Therefore, manufacturers have to be concerned with the
environmental impact of their products. In fact, the effort towards
environmental impact awareness is a universal concern, recognized
by government agencies. The Kyoto Protocol amendment to the United
Nations Framework Convention on Climate Change (UNFCCC) currently
signed by 156 nations is one example of a global effort to favor
safer environmental manufacturing over cost and efficiency. When
applied to deicing and anti-icing, consumers are increasingly
selective about the origins of the products they purchase. The 2004
Co-operative Bank's annual Ethical Consumerism Report
(www.co-operativebank.co.uk) disclosed a 30.3% increase in consumer
spending on ethical retail products (a general classification for
environmental safe, organic and fair trade goods) between 2003 and
2004 while total consumer spending during the same period rose only
3.7%.
[0004] Glycols such as ethylene glycol, propylene glycol,
1,3-butylene glycol, and 2-methyl-1,3-propanediol are biodegradable
compounds useful in compositions ranging from cosmetics and
personal care formulations to detergents to heat transfer
compositions. While biodegradability is an important factor in
protecting the environment, biodegradation of glycols derived from
fossil-based sources has the unavoidable consequence of releasing
previously fixed CO2 into the atmosphere. Thus, while glycols in
general are advantageous for their biodegradability, the resulting
global warming potential of fossil-based glycols during
biodegradation is significant.
[0005] Carbon dioxide is singled out as the largest component of
the collection of greenhouse gases in the atmosphere. The level of
atmospheric carbon dioxide has increased 50% in the last two
hundred years. Recent reports indicate that the current level of
atmospheric carbon dioxide is higher than the peak level in the
late Pleistocene, the epoch before modern humans (Siegenthaler, U.
et al. Stable Carbon Cycle-Climate Relationship During the Late
Pleistocene, Science, Vol. 310, no. 5752 (Nov. 25, 2005), pp.
1313-1317). Therefore, any further addition of carbon dioxide to
the atmosphere is thought to further shift the effect of greenhouse
gases from stabilization of global temperatures to that of heating.
Consumers and environmental protection groups alike have identified
industrial release of carbon into the atmosphere as the source of
carbon causing the greenhouse effect.
[0006] Greenhouse gas emission can occur at any point during the
lifetime of a product. Consumers and environmental groups consider
the full lifespan of a product when evaluating a product's
environmental impact. Consumers look for products that do not
contribute new carbon to the atmosphere considering the
environmental impact of production, use and degradation. Only
organic products composed of carbon molecules from plant sugars and
starches and ultimately atmospheric carbon are considered to not
further contribute to the greenhouse effect.
[0007] In addition to adding carbon dioxide to the atmosphere,
current methods of industrial production of glycols produce
contaminants and waste products that include among them sulfuric
acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, oxalic
acid tartaric acid, acetic acids, Alkali metals, alkaline earth
metals, transitional metals and heavy metals, including Iron,
cobalt, nickel, copper, silver, molybdenum, tungsten, vanadium,
chromium, rhodium, palladium, osmium, iridium, rubidium, and
platinum (U.S. Pat. Nos. 2,434,110, 5,034,134, 5,334,778, and
5,10,036).
[0008] Also of concern to consumers, especially consumers of
deicing and anti-icing products, is an individual's reaction to
such a product. The rate of development of hypersensitivity has
markedly increased in the US in the last two decades. Many of these
reactions are attributed to trace amount of substances. Other
reactions are of idiopathic origin. Consumers seek products that
are composed of ingredients of a more purified source and/or of all
natural composition.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a deicing or anti-icing
composition comprising 1,3-propanediol and an aqueous solution,
wherein said 1,3-propanediol has a bio-based carbon content of at
least 1%.
[0010] The present invention is further directed to a deicing or
anti-icing composition comprising 1,3-propanediol and a surfactant,
wherein said 1,3-propanediol has a bio-based carbon content of at
least 1%.
[0011] The present invention is also directed to a deicing or
anti-icing composition comprising 1,3-propanediol wherein said
1,3-propanediol has an ultraviolet absorption at 220 nm of less
than about 0.200 and at 250 nm of less than about 0.075 and at 275
nm of less than about 0.075.
[0012] The present invention is additionally directed to a deicing
or anti-icing composition comprising 1,3-propanediol wherein said
1,3-propanediol has a concentration of total organic impurities of
less than about 400 ppm.
[0013] The present invention is even further directed to a deicing
or anti-icing composition comprising 1,3-propanediol, wherein the
1,3-propanediol in said composition has an anthropogenic CO.sub.2
emission profile of zero upon biodegradation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a graph showing CO.sub.2 emissions for CO.sub.2
fixation from the atmosphere during photosynthesis for renewably
based 1,3-propanediol (Bio-PDO.TM.) (-1.7 kg CO.sub.2/kg product)
and CO.sub.2 release to the atmosphere during biodegradation (kg
CO.sub.2/kg product) for ethylene glycol (EG) (+1.4 kg CO.sub.2/kg
product), propylene glycol (PG) (+1.7 kg CO.sub.2/kg product),
fossil-based 1,3-propanediol (Chem-PDO) (+1.7 kg CO.sub.2/kg
product), and fermentatively-derived 1,3-propanediol (Bio-PDO.TM.)
(+1.7 kg CO.sub.2/kg product).
[0015] FIG. 2 is a graph showing that the net emissions of CO.sub.2
to the atmosphere for renewably based 1,3-propanediol (Bio-PDO) is
zero (0).
[0016] FIG. 3 is a table that shows the calculations for the data
shown in FIGS. 1 and 2.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Applicants specifically incorporate the entire content of
all cited references in this disclosure. Further, when an amount,
concentration, or other value or parameter is given as either a
range, preferred range, or a list of upper preferable values and
lower preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of any upper range limit
or preferred value and any lower range limit or preferred value,
regardless of whether ranges are separately disclosed. Where a
range of numerical values is recited herein, unless otherwise
stated, the range is intended to include the endpoints thereof, and
all integers and fractions within the range. It is not intended
that the scope of the invention be limited to the specific values
recited when defining a range.
[0018] Compositions disclosed herein comprise 1,3-propanediol,
having at least 1% bio-based carbon content, as greater as up to
100% of the glycol component of the composition. In one embodiment,
the 1,3-propanediol comprises substantially all of the glycol
component of the composition of the invention. In another
embodiment, the 1,3-propanediol comprises all of the glycol
component of the composition.
1,3-Propanediol
[0019] The terms "bioPDO", "biologically-derived, biodegradable
1,3-propanediol", "biologically derived 1,3-propanediol",
"renewably-based 1,3-propanediol", "renewably-based, biodegradable
1,3-propanediol," "biosourced, and "biologically-produced
1,3-propanediol" and similar terms as used here in refer to
1,3-propanediol derived from microorganism metabolism of
plant-derived sugars composed of carbon of atmospheric origin, and
not composed of fossil-fuel carbon.
Anthropogenic CO.sub.2 Emission Profile
[0020] Applicants' invention relates to deicing and anti-icing
compositions comprising renewably-based, biodegradable
1,3-propanediol, in which said renewably-based, biodegradable
1,3-propanediol has an anthropogenic CO.sub.2 emission profile of
zero (0). An "anthropogenic emission profile" means anthropogenic
CO2 emissions that are contributed to the atmosphere upon
biodegradation of a compound or composition. p
[0021] "Biodegradable" or "Biodegradability" means the capacity of
a compound to be broken down by living organisms to simple, stable
compounds such as carbon dioxide and water.
[0022] Whereas photosynthesis is the process of creating growing
matter through the conversion of carbon dioxide (CO.sub.2) and
water (H.sub.2O) into plant material through the action of the sun,
biodegradation is the process of converting organic material back
into CO.sub.2 and H.sub.2O through the activity of living
organisms.
[0023] There are many published test methods for measuring the
biodegradability of organic chemicals such as glycols. One
internationally recognized method is ASTM E1720-01, Standard Test
Method for Determining Ready, Ultimate Biodegradability of Organic
Chemicals in a Sealed Vessel CO.sub.2 Production Test.
[0024] Chemicals that demonstrate 60% biodegradation or better in
this test method will biodegrade in most aerobic environments and
are classified as ready biodegradable. All of the glycols referred
to in this document meet this criteria.
[0025] Calculations setting forth the finding that the
1,3-propanediol of the present invention provides no anthropogenic
COs emissions upon biodegradation is set forth below. A table in
support of these calculations is provided in FIG. 3.
[0026] When one molecule of 1,3-propanediol degrades, three
molecules of CO.sub.2 are released into the atmosphere. Because all
of these molecules of CO.sub.2 released during degradation from
"fermentatively-derived" 1,3-propanediol have an atmospheric
origin, the net release of CO.sub.2 to the atmosphere is thus zero.
Comparatively, because a fossil fuel-derived propylene glycol and
fossil-derived 1,3-propanediol contains three carbon atoms which
originate from a fixed carbon source (i.e., the fossil fuel),
degradation of one molecule of fossil fuel-derived propylene glycol
or 1,3-propanediol results in a net release of three molecules of
CO.sub.2 into the atmosphere. Similarly, because fossil
fuel-derived ethylene glycol contains two carbon atoms, which
originate from a fixed carbon source, degradation of one molecule
of fossil fuel-derived ethylene glycol results in a net release of
two molecules of CO.sub.2 into the atmosphere.
[0027] In order to quantify the CO.sub.2 released for one kilogram
of each ethylene glycol, propylene glycol, chemical 1,3-propanediol
and "fermentatively-derived" 1,3 propanediol (Bio-PDO.TM.), the
product weight (1 kg) is divided by its molecular weight. For each
carbon atom present in the molecule, one molecule of CO.sub.2 is
released. The molecules of CO.sub.2 are multiplied by the molecular
weight of CO.sub.2 (44 kg/kmole) to quantify the impact of CO.sub.2
release (kg) per one unit (kg) of product.
Fossil-Fuel Based Carbon Feedstock Release 1 kg of fossil fuel
derived ethylene glycol*(1 kmol EG/62.068 kg)*(2 kmol CO.sub.2/1
kmol EG)*(44 kg CO.sub.2/kmol CO.sub.2)=1.4 kg CO.sub.2 1 kg of
fossil fuel derived propylene glycol*(1 kmol PG/76.094 kg )*(3 kmol
CO.sub.2/1 kmol PG)*(44 kg CO.sub.2/kmol CO.sub.2)=1.7 kg CO.sub.2
1 kg of fossil fuel derived 1,3-propanediol*(1 kmol chem-PDO/76.094
kg*(3 kmol CO.sub.2/1 kmol chem-PDO)*(44 kg CO.sub.2/kmol
CO.sub.2)=1.7 kg CO.sub.2 Bio-Based Carbon Feedstock Balance
[0028] Capture: 1 kg of Bio-PDO.TM.*(1 kmol Bio-PDO.TM./76.094
kg)*(-3 kmol CO.sub.2/1 kmol Bio-PDO.TM.)*(44 kg CO.sub.2/kmol
CO.sub.2)=-1.7 kg CO.sub.2
[0029] Release: 1 kg of Bio-PDO.TM.*(1 kmol Bio-PDO.TM./76.094
kg)*(3 kmol CO.sub.2/1 kmol Bio-PDO.TM.)*(44 kg CO.sub.2/kmol
CO.sub.2)=1.7 kg CO.sub.2
[0030] Net: -1.7 kg+1.7 kg=0 kg
[0031] This Bio-based Carbon Feedstock Balance result demonstrates
that there are no anthropogenic CO2 emissions from the
biodegradation of the renewably sourced Bio-PDO. The term
"anthropogenic" means man-made or fossil-derived.
Bio-Based Carbon
[0032] "Carbon of atmospheric origin" as used herein refers to
carbon atoms from carbon dioxide molecules that have recently, in
the last few decades, been free in the earth's atmosphere. Such
carbons in mass are identifiable by the present of particular
radioisotopes as described herein. "Green carbon", "atmospheric
carbon", "environmentally friendly carbon", "life-cycle carbon",
"non-fossil fuel based carbon", "non-petroleum based carbon",
"carbon of atmospheric origin", and "biobased carbon" are used
synonymously herein.
[0033] "Carbon of fossil origin" as used herein refers to carbon of
petrochemical origin. Such carbon has not been exposed to UV rays
as atmospheric carbon has, therefore masses of carbon of fossil
origin has few radioisotopes in their population. Carbon of fossil
origin is identifiable by means described herein. "Fossil fuel
carbon", "fossil carbon", "polluting carbon", "petrochemical
carbon", "petro-carbon" and carbon of fossil origin are used
synonymously herein.
[0034] The abbreviation "IRMS" refers to measurements of CO2 by
high precision stable isotope ratio mass spectrometry.
[0035] The term "carbon substrate" means any carbon source capable
of being metabolized by a microorganism wherein the substrate
contains at least one carbon atom.
[0036] "Renewably-based" denotes that the carbon content of the
1,3-propanediol is from a "new carbon" source as measured by ASTM
test method D 6866-05 Determining the Biobased Content of Natural
Range Materials Using Radiocarbon and Isotope Ratio Mass
Spectrometry Analysis, incorporated herein by reference. This test
method measures the C-14/C-12 isotope ratio in a sample and
compares it to the C-14/C-12 isotope ratio in a standard 100%
biobased material to give percent biobased content of the sample.
"Biobased materials" are organic materials in which the carbon
comes from recently (on a human time scale) fixated CO.sub.2
present in the atmosphere using sunlight energy (photosynthesis).
On land, this CO.sub.2 is captured or fixated by plant life (e.g.,
agricultural crops or forestry materials). In the oceans, the
CO.sub.2 is captured or fixated by photosynthesizing bacteria or
phytoplankton. A biobased material has a C-14/C-12 isotope ratio in
range of from 1:0 to greater than 0:1. Contrarily, a fossil-based
material, has a C-14/C-12 isotope ratio of 0:1.
[0037] A small amount of the carbon dioxide in the atmosphere is
radioactive. This 14C carbon dioxide is created when nitrogen is
struck by an ultra-violet light produced neutron, causing the
nitrogen to lose a proton and form carbon of molecular weight 14
which is immediately oxidized in carbon dioxide. This radioactive
isotope represents a small but measurable fraction of atmospheric
carbon. Atmospheric carbon dioxide is cycled by green plants to
make organic molecules during the process known as photosynthesis.
The cycle is completed when the green plants or other forms of life
metabolize the organic molecules producing carbon dioxide which is
released back to the atmosphere. Virtually all forms of life on
Earth depend on this green plant production of organic molecule to
produce the chemical energy that facilitates growth and
reproduction. Therefore, the 14C that exists in the atmosphere
becomes part of all life forms, and their biological products.
These renewably based organic molecules that biodegrade to CO2 do
not contribute to global warming as there is no net increase of
carbon emitted to the atmosphere. In contrast, fossil fuel based
carbon does not have the signature radiocarbon ratio of atmospheric
carbon dioxide.
[0038] Atmospheric origin and fixed carbon source as used herein
are relative terms in that the time period of when CO2 is of
atmospheric or fixed origin relates to the life cycle of the
1,3-propanediol. Thus, while it is quite possible that, at one
time, carbon from a fossil fuel was found in the atmosphere (and,
as a corollary, that atmospheric CO2 may one day be incorporated
into a fixed carbon source), for purposes herein carbon is
considered to be from a fixed carbon source until it is released
into the atmosphere by degradation.
[0039] Assessment of the renewably based carbon in a material can
be performed through standard test methods. Using radiocarbon and
isotope ratio mass spectrometry analysis, the biobased content of
materials can be determined. ASTM International, formally known as
the American Society for Testing and Materials, has established a
standard method for assessing the biobased content of materials.
The ASTM method is designated ASTM-D6866.
[0040] The application of ASTM-D6866 to derive a "biobased content"
is built on the same concepts as radiocarbon dating, but without
use of the age equations. The analysis is performed by deriving a
ratio of the amount of radiocarbon (14C) in an unknown sample to
that of a modem reference standard. The ratio is reported as a
percentage with the units "pMC" (percent modern carbon). If the
material being analyzed is a mixture of present day radiocarbon and
fossil carbon (containing no radiocarbon), then the pMC value
obtained correlates directly to the amount of Biomass material
present in the sample.
[0041] The modern reference standard used in radiocarbon dating is
a NIST (National Institute of Standards and Technology) standard
with a known radiocarbon content equivalent approximately to the
year AD 1950. AD 1950 was chosen since it represented a time prior
to thermo-nuclear weapons testing which introduced large amounts of
excess radiocarbon into the atmosphere with each explosion (termed
"bomb carbon"). The AD 1950 reference represents 100 pMC.
[0042] "Bomb carbon" in the atmosphere reached almost twice normal
levels in 1963 at the peak of testing and prior to the treaty
halting the testing. Its distribution within the atmosphere has
been approximated since its appearance, showing values that are
greater than 100 pMC for plants and animals living since AD 1950.
It's gradually decreased over time with today's value being near
107.5 pMC. This means that a fresh biomass material such as corn
could give a radiocarbon signature near 107.5 pMC.
[0043] Combining fossil carbon with present day carbon into a
material will result in a dilution of the present day pMC content.
By presuming 107.5 pMC represents present day biomass materials and
0 pMC represents petroleum derivatives, the measured pMC value for
that material will reflect the proportions of the two component
types. A material derived 100% from present day soybeans would give
a radiocarbon signature near 107.5 pMC. If that material was
diluted with 50% petroleum derivatives, it would give a radiocarbon
signature near 54 pMC.
[0044] A biomass content result is derived by assigning 100% equal
to 107.5 pMC and 0% equal to 0 pMC. In this regard, a sample
measuring 99 pMC will give an equivalent biobased content result of
93%.
[0045] A sample of "fermentatively-derived" 1,3-propanediol was
submitted by DuPont to Iowa State University for biobased content
analysis using ASTM method D 6866-05. The results received from
Iowa State University demonstrated that the above sample was 100%
bio-based content (ref: Norton, Glenn. Results of Radiocarbon
Analyses on samples from DuPont Bio-Based Materials--reported Jul.
8, 2005).
[0046] Assessment of the materials described herein were done in
accordance with ASTM-D6866. The mean values quoted in this report
encompasses an absolute range of 6% (plus and minus 3% on either
side of the biobased content value) to account for variations in
end-component radiocarbon signatures. It is presumed that all
materials are present day or fossil in origin and that the desired
result is the amount of biobased component "present" in the
material, not the amount of biobased material "used" in the
manufacturing process.
[0047] Results of Radiocarbon Analyses on Samples from DuPont
Bio-Based Materials
[0048] Reported Jul. 8, 2005 TABLE-US-00001 PRODUCT BIOBASED
CONTENT (%) 1,3-Propanediol 100
[0049] There may be certain instances wherein a deicing or
anti-icing composition of the invention may comprise a combination
of a biologically-derived 1,3-propanediol and one or more non
biologically-derived glycol components, such as, for example,
chemically synthesized 1,3-propanediol. In such occasions, it may
be difficult, if not impossible to determine which percentage of
the glycol composition is biologically-derived, other than by
calculating the bio-based carbon content of the glycol component.
In this regard, in the deicing and anti-icing compositions of the
invention, the glycol component, and in particular, the
1,3-propanediol, can comprise at least about 1% bio-based carbon
content up to 100% bio-based carbon content, and any percentage
therebetween.
Purity
[0050] "Substantially purified," as used by applicants to describe
the biologically-produced 1,3-propanediol produced by the process
of the invention, denotes a composition comprising 1,3-propanediol
having at least one of the following characteristics: 1) an
ultraviolet absorption at 220 nm of less than about 0.200 and at
250 nm of less than about 0.075 and at 275 nm of less than about
0.075; or 2) a composition having L*a*b* "b*" color value of less
than about 0.15 and an absorbance at 270 nm of less than about
0.075; or 3) a peroxide composition of less than about 10 ppm; or
4) a concentration of total organic impurities of less than about
400 ppm.
[0051] A "b*" value is the spectrophotometrically determined
"Yellow Blue measurement as defined by the CIE L*a*b* measurement
ASTM D6290.
[0052] The abbreviation "AMS" refers to accelerator mass
spectrometry.
[0053] By the acronym "NMR" is meant nuclear magnetic
resonance.
[0054] By the terms "color" and "color bodies" is meant the
existence of visible color that can be quantified using a
spectrocolorimeter in the range of visible light, using wavelengths
of approximately 400-800 nm, and by comparison with pure water.
Reaction conditions can have an important effect on the nature of
color production. Examples of relevant conditions include the
temperatures used, the catalyst and amount of catalyst. While not
wishing to be bound by theory, we believe color precursors include
trace amounts of impurities comprising olefinic bonds, acetals and
other carbonyl compounds, peroxides, etc. At least some of these
impurities may be detected by such methods as UV spectroscopy, or
peroxide titration.
[0055] "Color index" refers to an analytic measure of the
electromagnetic radiation-absorbing properties of a substance or
compound.
[0056] Biologically-derived 1,3-propanediol useful in deicing and
anti-icing compositions disclosed herein has at least one of the
following characteristics: 1) an ultraviolet absorption at 220 nm
of less than about 0.200 and at 250 nm of less than about 0.075 and
at 275 nm of less than about 0.075; or 2) a composition having
L*a*b* "b*" color value of less than about 0.15 and an absorbance
at 270 nm of less than about 0.075; or 3) a peroxide composition of
less than about 10 ppm; or 4) a concentration of total organic
impurities of less than about 400 ppm. A "b*" value is the
spectrophotometrically determined Yellow Blue measurement as
defined by the CIE L*a*b* measurement ASTM D6290.
[0057] The level of 1,3-propanediol purity can be characterized in
a number of different ways. For example, measuring the remaining
levels of contaminating organic impurities is one useful measure.
Biologically-derived 1,3-propanediol can have a purity level of
less than about 400 ppm total organic contaminants; preferably less
than about 300 ppm; and most preferably less than about 150 ppm.
The term ppm total organic purity refers to parts per million
levels of carbon-containing compounds (other than 1,3-propanediol)
as measured by gas chromatography.
[0058] Biologically-derived 1,3-propanediol can also be
characterized using a number of other parameters, such as
ultraviolet light absorbance at varying wavelengths. The
wavelengths 220 nm, 240 nm and 270 nm have been found to be useful
in determining purity levels of the composition.
Biologically-derived 1,3-propanediol can have a purity level
wherein the UV absorption at 220 nm is less than about 0.200 and at
240 nm is less than about 0.075 and at 270 nm is less than about
0.075.
[0059] Biologically-derived 1,3-propanediol can have a b* color
value (CIE L*a*b*) of less than about 0.15.
[0060] The purity of biologically-derived 1,3-propanediol
compositions can also be assessed in a meaningful way by measuring
levels of peroxide. Biologically-derived 1,3-propanediol can have a
concentration of peroxide of less than about 10 ppm.
[0061] It is believed that the aforementioned purity level
parameters for biologically-derived and purified 1,3-propanediol
(using methods similar or comparable to those disclosed in U.S.
Patent Application No. 2005/0069997) distinguishes such
compositions from 1,3-propanediol compositions prepared from
chemically purified 1,3-propanediol derived from petroleum sources,
as per the prior art.
Fermentation
[0062] "Biologically produced" means organic compounds produced by
one or more species or strains of living organisms, including
particularly strains of bacteria, yeast, fungus and other microbes.
"Bio-produced" and biologically produced are used synonymously
herein. Such organic compounds are composed of carbon from
atmospheric carbon dioxide converted to sugars and starches by
green plants.
[0063] "Biologically-based" means that the organic compound is
synthesized from biologically produced organic components. It is
further contemplated that the synthesis process disclosed herein is
capable of effectively synthesizing other monoesters and diesters
from bio-produced alcohols other than 1,3-propanediol; particularly
including ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, dipropylene diol, tripropylene diol, 2-methyl
1,3-propanediol, neopentyl glycol and bisphenol A. "Bio-based", and
"bio-sourced"; "biologically derived"; and "bio-derived" are used
synonymously herein.
[0064] "Fermentation" as used refers to the process of metabolizing
simple sugars into other organic compounds. As used herein
fermentation specifically refers to the metabolism of plant derived
sugars, such sugar are composed of carbon of atmospheric
origin.
[0065] Biologically-derived 1,3-propanediol can be obtained based
upon use of the fermentation broth ("fermentatively-derived")
generated by a genetically-engineered Escherichia coli (E. coli)
previously disclosed in, for example, U.S. Pat. No. 5,686,276.
However, other single organisms, or combinations of organisms, may
be used to biologically produce 1,3-propanediol, using organisms
that have been genetically-engineered according to methods known in
the art. "Fermentation" refers to a system that catalyzes a
reaction between substrate(s) and other nutrients to product(s)
through use of a biocatalyst. The biocatalysts can be a whole
organism, an isolated enzyme, or any combination or component
thereof that is enzymatically active. Fermentation systems useful
for producing and purifying biologically-derived 1,3-propanediol
are disclosed in, for example, Published U.S. Patent Application
No. 2005/0069997 incorporated herein by reference.
[0066] The biologically derived 1,3-propanediol (Bio-PDO) for use
in the current invention, produced by the process described herein,
contains carbon from the atmosphere incorporated by plants, which
compose the feedstock for the production of Bio-PDO. In this way,
the Bio-PDO used in the compositions of the invention contains only
renewable carbon, and not fossil fuel based, or petroleum based
carbon. Therefore the compositions of the invention have less
impact on the environment as the propanediol used in the
compositions does not deplete diminishing fossil fuels and, upon
degradation releases carbon back to the atmosphere for use by
plants once again. Thus, the present invention can be characterized
as more natural and having less environmental impact than similar
compositions comprising petroleum based glycols.
[0067] Moreover, as the purity of the Bio-PDO utilized in the
compositions of the invention is higher than chemically synthesized
1,3-propanediol and other glycols, risk of introducing impurities
that may cause irritation is reduced by its use over commonly used
glycols, such as propylene glycol.
[0068] This 1,3-propanediol of the invention can be isolated from
the fermentation broth and is incorporated into deicing and
anti-icing compositions of the invention, by processes as are known
to those of ordinary skill in the applicable art.
Renewably-Based, Biodegradable 1,3-propanediol-Containing
Compositions
[0069] As mentioned above, Bio-PDO can be incorporated into
numerous compositions as a glycol component. For example, Bio-PDO
can be part of or the sole glycol component of deicing compositions
and anti-icing compositions.
[0070] It is contemplated herein that other renewably-based or
biologically-derived glycols, such as ethylene glycol or 1,2
propylene glycol, diethylene glycol, triethylene glycol among
others, can be used in the anti-icing and deicing compositions of
the present invention.
[0071] The deicing/anti-icing compositions can be used in any
application requiring deicing and/or anti-icing. In some
embodiments, the compositions are used for the removal of, and/or
time-limited protection against, deposits of frost, ice, and/or
snow on exterior aircraft surfaces prior to take off, or on
roadway/runway surfaces. The compositions can be applied through a
commercial deicing/anti-icing vehicle system to the surfaces at
pressures and flow rates normal for intended use.
[0072] In addition to application to aircraft, the compositions can
also be used for other anti-icing/deicing applications, such as,
surfaces of, for example, airport pavements, roadways, walkways,
sidewalks, bridges, entrances, electrical tower structures and
their components, electricity transmission lines, canals, locks,
vessels, nautical components, railroad switches, and motor
vehicles. In addition, the compositions can be used in applications
such as birdbaths, outdoor fountains, decorative ponds, and other
outdoor areas where water freezing would be aesthetically or
functionally unacceptable. In these applications the fluids can
prevent water from freezing during the winter in cold climates with
reduced biological risk to wildlife or domestic animals.
[0073] It is also envisioned that the compositions of the present
invention can be used in either a liquid or a solid format. For
instance, the compound can be prepared as a liquid and sprayed on
or spread on surfaces. Alternatively, it can be prepared in a solid
form and employed as a powder. Optionally, the solid may be further
processed using methods well known in the art, such as, for
example, pelletizing, prilling, flaking, or macerating to provide
the formulation in a final useable powdered or granular form. Any
of the binders known to those skilled in the art optionally may be
present and may either be inert or may be comprised of components
that actively help lower the freezing point. For example, cinders,
sawdust, sand, gravel, sugars, maltodextrins and mixtures thereof
and the like can be used.
[0074] In the methods of the present invention, the deicing and/or
anti-icing compositions of the present invention are applied, such
as by spraying or injecting for liquid forms.
[0075] In the anti-icing or deicing compositions of the invention,
the Bio-PDO or other bio-derived glycol component can be the major
component of the composition, present in amounts up to 100% by
weight based on the weight of the total composition. The amount of
Bio-PDO used in the products is generally the balance after adding
one or more of surfactant, corrosion inhibitors, water, and any
optional ingredients. Deicing/anti-icing fluids preferably contain
from about 10% to about 95% Bio-PDO by weight, and more preferably
from about 25% to about 92%. A typical formulation for aircraft
deicing/anti-icing may include, but is not limited to, the
following components: 25-95% by weight of Bio-PDO or mixture
thereof; and up to 1% each of the following components: at least
one surfactant or surfactant blend, at least one corrosion
inhibitor, a pH control agent, a thickening agent, and a dye. Water
can make up the balance of this formulation. Further details on
alternative formulations and ingredients is provided below.
[0076] In certain embodiments, such as those containing glycerol in
combination with Bio-PDO, the compositions of the invention
preferably contain from about 10% to about 88% glycerol and as
such, from as little as about 1% to about 30% Bio-PDO.
Functional and Other Ingredients
[0077] The deicing/anti-icing products of the invention can include
one or more functional and other ingredients. Functional and other
ingredients useful herein may be categorized or described herein by
their benefit or their postulated mode of action in the deicing or
anti-icing composition. However, it is to be understood that the
functional and other ingredients useful herein can in some
instances provide more than one benefit or operate via more than
one mode of action. Therefore, classifications herein are made for
the sake of convenience and are not intended to limit an ingredient
to the particularly stated application or applications listed.
Surfactants
[0078] A preferred surfactant is a nonionic surfactant; anionic,
cationic, and amphoteric (zwitterionic) surfactants are less
preferred. Some nonlimiting examples of suitable nonionic
surfactants are: alkylphenol ethoxylates (C.sub.12 or lower,
C.sub.8 or lower preferred); fatty or oxo-alcohol
polyethyleneglycol ethers (C.sub.16 or lower, C.sub.6 or lower
preferred); ethylene oxide-propylene oxide polymers (C.sub.80 or
lower, C.sub.2 or lower preferred); fatty alcohol polyglycol ethers
(C.sub.18 or lower, C.sub.8 or lower preferred); polyethoxylates
such as polyoxyethylene ethers; polypropyloxylates such as
polyoxypropylene ethers; sugar-based surfactants such as alkyl
glycosides (e.g., alkyl benzene and tert-butoxyethanol); ethers of
C.sub.1 to C.sub.8 polyethylene oxide repeat units of 2 to 50
polyethylene oxide units (low carbon alkyl group and somewhat
higher carbon ethoxylate group preferred); polyvinyl alcohols
having MW 1000-10,000; and polyvinyl pyrrolidones.
[0079] The nonionic surfactants can be selected from
polyoxyalkylene ethers. Some preferred polyoxyalkylene ethers are
ethers of C.sub.12 to C.sub.18 alcohols with polyethylene oxide
repeat units of 2 to 100 polyethylene oxide units. Such surfactants
include, for example, the Brij..TM.. series of surfactants
manufactured by ICI (e.g., Brij 30, 35, 52, 56, 58, 72, 76, 78, 92,
97, 98 and 700). Brij 35 is polyoxyethylene lauryl ether, 718
average MW, having the chemical formula:
CH.sub.3(CH.sub.2).sub.11(CH.sub.2CH.sub.20).sub.xH, where x on
average is 23.
[0080] The fluids can contain any suitable amount of surfactant.
Preferably, the fluids contain from about 0.01% to about 0.9%
surfactant by weight, and more preferably from about 0.05% to about
0.5%.
pH Control Agent
[0081] The deicing/anti-icing compositions of the invention can
optionally include one or more pH control agents to maintain the
fluid at constant pH. The compositions can have any suitable pH.
The pH of the compositions can range anywhere from about 3.5 to
about 12, and preferably from about 6 to about 9. The desired pH
can be obtained using inorganic bases such as sodium hydroxide,
ammonium hydroxide and potassium hydroxide, or amines such as
triethanol amine, diethanol amine or monoethanol amine.
[0082] Some nonlimiting examples of suitable buffers include:
phosphate salts (K.sup.+, NH.sub.4.sup.+); pyrophosphates
(Na.sup.+, K.sup.+, NH.sub.4.sup.+); metaphosphates (Na.sup.+,
K.sup.+, NH.sub.4.sup.+); carbonic acid and its salts (Na.sup.+l ,
K.sup.+, NH.sub.4.sup.+); hydroxyl ammonium (Na.sup.+, K.sup.+,
NH.sub.4.sup.+); adidic acid and its salts (Na.sup.+, K.sup.+,
NH.sub.4.sup.+); maleic acid and its salts (Na.sup.+, K.sup.+,
NH.sub.4.sup.+); and ascorbic acid and its salts (Na.sup.+,
K.sup.+, NH.sub.4.sup.+).
Defoamers
[0083] Defoamers may also be employed. Any commercially available
defoamer or antifoamer can be used, but particularly preferred
defoamers are a silicone defoamer of Union Carbide Corporation sold
under the trademark SAG, and FOAMBAN.TM. defoamer available from
Ultra Additives Inc., Patterson, N.J. The amount of defoamer to be
used is preferably in the range of from about 0.05% to about 0.5%
by weight based on the weight of the total composition.
Corrosion Inhibitors
[0084] Suitable corrosion inhibitors are known to the art, and
typically comprise mixtures of various functional materials, e.g.,
buffers, chelating agents, and the like, esters of inorganic acids
such as the phosphorus and boron, aromatic triazoles such as tolyl-
and benzyltriazole, and the like, in one or more solvents. A
preferred anticorrosion mixture is that product sold by Sandoz
under the designation "Sandocorin 8132". Those having skill in the
art understand that selection of appropriate corrosion inhibitor
may be made based upon the type of surfaces which the present
compositions are likely to come in contact with, and how long and
under what conditions they are likely to remain on that
surface.
[0085] Suitable corrosion inhibitors include those belonging to the
group comprising inorganic metal salts, alkali metal salts of fatty
acids, monoalkyl amines and dialkyl amines optionally
alkoxylated--and salts thereof, alkanol amines--optionally
alkoxylated and salts thereof, esters of phosphorus acid or of
phosphoric acid, and triazoles. The amount of corrosion inhibitor
to be used is preferably in the range of from about 0.05% to about
0.8% by weight based on the weight of the total composition.
Thickening Agents
[0086] Thickening agents can be used in the compositions of the
invention, and often comprise polymeric water-activated thickening
agents. Thickening agents will typically comprise between 0.1 and
15.0 weight percent of the total composition. Examples include
polysaccharide thickeners, natural gum thickeners, marine algae
colloids, and cellulose ether thickeners. A preferred thickener is
a polysaccharide known generically as Xanthan Gum.
Oils
[0087] The composition can optionally contain at least one
non-polar oil, such as aliphatic and aromatic oils such as mineral
oil, paraffin oil, silicone oil, and propylene oxide/ethylene oxide
copolymers. The amount of such oils is frequently in the range of
from about 0.01% to about 5% by weight based on the total weight of
the composition. The preferred range is between 0.1% to 1.0% by
weight based on the total weight of the composition.
Thermal Stabilizing Agents
[0088] The deicing/anti-icing products can further include a
material that improves the thermal stability of the material. Any
suitable material having these properties can be used, for example
certain of the phosphate salts. A particular example is a mixture
of mono-basic sodium phosphate and di-basic sodium phosphate, such
as the monohydrate mono-basic and heptahydrate di-basic sodium
phosphates.
[0089] The products can contain any suitable amount of the
buffer/freezing point depressant. The fluids preferably contain
from about 0.02% to about 2% mono-basic sodium phosphate and from
about 0.02% to about 2% di-basic sodium phosphate by weight, more
preferably from about 0.3% to about 1.5% mono-basic sodium
phosphate and from about 0.3% to about 1.5% di-basic sodium
phosphate.
Anti-Microbial Aaents
[0090] The deicing/anti-icing products can optionally include one
or more anti-microbial agents. Some nonlimiting examples of
suitable anti-microbial agents include: sodium azide; quaternary
ammonium compounds (e.g.,
2-methyl-4,5-trimethylene-4-isothizoline-3-one; n-alkyl dimethyl
benzyl ammonium X.sup.- [where alkyl carbon number is C.sub.12-18
]; n-alkyl trimethyl ammonium X.sup.- [where alkyl carbon number is
C.sub.12-18]; dialkyl dimethyl ammonium X.sup.- [where alkyl carbon
number is C.sub.12-18]; octyl decyl dimethyl ammonium X.sup.-
[where X.sup.- is Cl.sup.-, Br.sup.-, I.sub.3.sup.-,
HCO.sub.3.sup.-, CO.sub.3.sup.2-, phosphates, phosphonates, OH,
carboxylates, polycarboxylates]); M.sup.+ benzoates (where M.sup.+
is Na.sup.+, K.sup.+, NH.sub.4.sup.+; alkyl dimethyl benzyl
ammonium chlorides; and alkyl dimethyl benzyl/ethyl benzyl ammonium
chlorides.
Fire Retardants
[0091] The deicing/anti-icing products can also optionally include
one or more flame and/or corrosion inhibitors. Some common
additives used for both fire and corrosion inhibition include
sodium tolyltriazole and 1 H-benzotriazole, methyl.
Vinylpyrrolidone
[0092] In another embodiment of the invention, the
deicing/anti-icing fluids include a biobased freezing point
depressant as described above, in combination with a
vinylpyrrolidone polymer having a molecular weight between about
10,000 and about 700,000, and water. By "vinylpyrrolidone polymer"
is meant a homopolymer or a copolymer of vinylpyrrolidone, or a
derivative thereof. Suitable derivatives of vinylpyrrolidine
polymer may include alkylated polyvinylpyrrolidones, 2-menthyl.
Preferably, the vinylpyrrolidone polymer is
polyvinylpyrrolidone.
[0093] The vinylpyrrolidone polymer preferably has a molecular
weight between about 10,000 and about 700,000, and preferably not
greater than about 360,000. It is believed that higher molecular
weight vinylpyrrolidone polymers may produce deicing/anti-icing
fluids having less desirable properties, particularly for aircraft
and runway deicing.
[0094] The deicing/anti-icing products can contain any suitable
amount of the vinylpyrrolidone polymer. Typically, the products
contain about 5% or less vinylpyrrolidone polymer, and usually
between about 0.1% and about 3%.
[0095] Advantageously, the vinylpyrrolidone polymer often functions
as both a thickener and a surfactant in the fluid. Consequently,
products having desirable properties can be produced using a
minimal number of ingredients. However, optionally the products can
also contain other ingredients such as an antioxidant and/or a
second surfactant.
Aqueous Solvents
[0096] The deicing/anti-icing products can also include an aqueous
solvent (i.e. water) in any suitable amount, usually in an amount
of from about 30% to about 70% by weight. It should be noted that
the percentages of ingredients given herein are based on a
ready-to-use products. The products of the invention can also be
provided in a concentrate formulation, in which case the percentage
of aqueous solvent will decrease (e.g., the concentrate may contain
from about 5% to about 20% water) and the percentages of other
materials will increase accordingly.
Colorants or Dyes
[0097] The deicing/anti-icing products can also include an
colorants or dyes in any suitable amount, usually in an amount up
to 0.25% by volume of the formulation.
Esters
[0098] Esters can function as many of the above noted ingredients.
While those in those having skill in the art can readily determine
which esters are most appropriate to provide a particularly desired
function, applications specifically note that esters used in this
invention may include the esters produced, including all the
appropriate conjugate mono and diesters, from biologically-derived
1,3 propanediol using organic carboxylic acids. Some esters in
particular that are produced include propanediol distearate and
monostearate, propandiol dilaurate and monolaurate, propanediol
dioleate and monooleate, propanediol divalerate and monovalerate,
propanediol dicaprylate and monocaprylate, propanediol dimyristate
and monomyristate, propanediol dipalmitate and monopalmitate,
propanediol dibehenate and monobehenate, propanediol adipate,
propanediol maleate, propanediol dioxalate, propanediol dibenzoate,
propanediol diacetate, and all mixtures thereof.
Miscellaneous Additives
[0099] The composition may also contain various other functional
ingredients such as UV inhibitors, odor-modification agents,
stabilizers and the like. Each of these components will typically
comprise less than 1.0 weight percent of the total composition.
[0100] In specific applications, certain embodiments of the present
invention are especially preferred due to certain regulatory or
industry guidelines. For example, in the deicing and/or anti-icing
of aircraft, it is preferred to use deicing and/or anti-icing
fluids of Bio-PDO, water; a mixture of Bio-PDO and other
bio-derived glycols and water, or a mixture of Bio-PDO,
petrochemically derived glycols, and water agents of methyl
glucoside; a mixture of sorbitol and Bio-PDO; or a mixture of
methyl glucoside, sorbitol and Bio-PDO with sodium lactate and/or
potassium lactate.
[0101] For the deicing and/or anti-icing of runways, it may be
preferable to use deicing and/or anti-icing agents of sodium
lactate; potassium lactate; a mixture of sodium lactate and
potassium lactate; a hydroxyl-containing organic compound in
combination with sodium lactate, potassium lactate and/or potassium
acetate as well as Bio-PDO; a mixture of sodium lactate and/or
potassium lactate with potassium acetate; or potassium carbonate
and Bio-PDO.
[0102] For de-icing and/or anti-icing of pre-harvest fruits and
vegetables, such as fruit trees or grape vines, it may be
preferable to use de-icing and/or anti-icing agents of a
hydroxyl-containing organic compound in combination with Bio-PDO
and an organic acid salt, particularly a lactate salt.
[0103] The deicing and anti-icing compositions of the invention can
contain any natural ingredients where appropriate. Natural
ingredients include any natural or nature-derived ingredients
similar in composition or in function to any of the ingredients
listed above.
[0104] All of the compositions and methods disclosed and claimed
herein can be made and executed without undue experimentation in
light of the present disclosure. While the compositions and methods
of the present disclosure have been described in terms of preferred
embodiments, it will be apparent to those of skill in the art that
variations may be applied to the compositions and methods and in
the steps or in the sequence of steps of the method described
herein without departing from the concept, spirit, and scope of the
invention. More specifically, it will be apparent that certain
agents, which are chemically related, may be substituted for the
agents described herein while the same or similar results would be
achieved. All such similar substitutes and modifications apparent
to those skilled in the art are deemed to be within the spirit,
scope, and concept of the invention as defined by the appended
claims.
EXAMPLES
[0105] The present invention is further defined in the following
Examples. It should be understood that these Examples, while
indicating preferred embodiments of the invention, are given by way
of illustration only. From the above discussion and these Examples,
one skilled in the art can ascertain the preferred features of this
invention, and without departing from the spirit and scope thereof,
can make various changes and modifications of the invention to
adapt it to various uses and conditions.
Example 1
[0106] TABLE-US-00002 Aircraft Deicing Fluid Ingredients: % Wt.
Bio-PDO 92 Water 7.14 Polyethylene glycol ether 0.2 EO/PO
alkoxylate 0.2 KOH (50% solution) .06 Sandocorin 8132C 0.4
Example 2
[0107] TABLE-US-00003 Aircraft Deicing Fluid Ingredients: % Wt.
Bio-PDO 45.5 Water 53.165 Tolytriazole 0.4 Silicon anti-foamer 0.2
Potassium Hydroxide .035 Triethanolamine 0.3 Sodium arylalkyl
sulfonate 0.4
Example 3
[0108] TABLE-US-00004 Aircraft runway deicing composition
Ingredient Wt, % Alkali metal carboxylate 20-25% Alkali earth metal
carboxylate 1-15% Bio-PDO 1-35% Alkali metal phosphate 0.01-1%
Alkali metal silicate 0.01-1% Triazole 0.01-1%
Example 4
[0109] TABLE-US-00005 Aircraft runway deicing composition
Ingredient Wt, % Alkali metal carboxylate 1-40% Alkali earth metal
carboxylate 1-25% Bio-PDO 1-35% Alkali metal phosphate 0.01-1%
Alkali metal silicate 0.01-1% Triazole 0.01-1% Water q.s. to
100%
Example 5
[0110] TABLE-US-00006 Deicer/anti-icer for aircraft Ingredient Wt,
% Water 41% Bio-PDO 50% Polysaccharide 3% Corrosion inhibitors
6%
Example 6
[0111] TABLE-US-00007 Deicers for polyurethane foam-lined LPG tanks
Ingredient Wt, % Isopropanol 40% Bio-PDO 60%
Example 7
Liquid Carboxylate Deicer Composition
[0112] The liquid deicer compounds suitable for roadways, runways,
and bridges include: (a) aqueous carboxylate salt of alkali metal,
especially as formate, propionate, and/or lactate; (b) corrosion
inhibitors for protection of galvanized steel; (c) auxiliary
corrosion inhibitors for nonferrous metals, esp. Al alloys; and (d)
optional Bio-PDO. The corrosion inhibitor is preferably a
polyvalent metal compd., esp. La acetate hydrate or a mixed
lanthanide salt sol. in water, or optionally a Mg-ion compd. and/or
a sulfide salt. The deicer optionally includes 50-10,000 ppm of
tolyltriazole as auxiliary inhibitor for nonferrous metal surfaces.
The typical aqueous deicer contains potassium acetate 50%,
tolyltriazole 0.15-0.75%, lanthanide nitrate hexahydrate 1.0-3.0%,
and trimercaptotriazine tri-Na salt 10.10-0.75%, water q.s. to
100%.
Example 8
Water-Activated, Exothermic Chemical Deicing Formulation
[0113] Deicing compositions are provided for removing ice from a
surface which include either succinic acid or succinic anhydride,
or both, and a neutralizing base such as sodium hydroxide,
potassium hydroxide, or ammonium hydroxide wherein the deicing
compositions when mixed with water produce succinate salts in a
reaction that rapidly releases sufficient heat to melt the ice on
the surface and the succinate salts act as a deicer and freeze
point depressant. The deicing compositions may further include
Bio-PDO which inhibits reformation of the ice on the deiced
surface. The deicing compositions are suitable and effective for
airport applications in which corrosion of aircraft alloys and
concrete runways are of concern.
Example 9
Anti-Icing Fluid or Deicing Fluid
[0114] The title non-electrolytic, non-toxic, biodegradable
anti-icing or deicing composition comprises: (a) water; (b) a
non-toxic freeze point depressant selected from the group
consisting of C2-6 monohydric alcohols, Bio-PDO, mono-Me or Et
ethers of C3-12 polyhydric alcohols or mixtures thereof, (c) a
nontoxic thickener. The composition is a continuous single phase
liquid that exhibits pseudoplasticity, and is useful on the
surfaces of, for example, aircraft, airport pavements, roadways,
walkways, bridges, entrances, structures, canals, locks,
components, vessels, nautical components, railroad switches, and
motor vehicles. A typical composition contained water, Bio-PDO.TM.
and/or propanol and xanthan.
* * * * *