U.S. patent application number 10/341540 was filed with the patent office on 2003-09-11 for environmentally benign anti-icing or deicing fluids.
Invention is credited to Johnson, Axel, Ricks, William, Sapienza, Richard.
Application Number | 20030168625 10/341540 |
Document ID | / |
Family ID | 32711533 |
Filed Date | 2003-09-11 |
United States Patent
Application |
20030168625 |
Kind Code |
A1 |
Sapienza, Richard ; et
al. |
September 11, 2003 |
Environmentally benign anti-icing or deicing fluids
Abstract
Deicing compositions comprised of hydroxyl-containing organic
compounds and/or organic acid salts are disclosed.
Inventors: |
Sapienza, Richard;
(Shoreham, NY) ; Johnson, Axel; (North Babylon,
NY) ; Ricks, William; (Westerville, OH) |
Correspondence
Address: |
Alan B. Clement, Esq.
HEDMAN & COSTIGAN, P.C.
1185 Avenue of the Americas
New York
NY
10036
US
|
Family ID: |
32711533 |
Appl. No.: |
10/341540 |
Filed: |
January 13, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10341540 |
Jan 13, 2003 |
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09675495 |
Sep 29, 2000 |
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6506318 |
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09675495 |
Sep 29, 2000 |
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09436811 |
Nov 9, 1999 |
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6129857 |
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09436811 |
Nov 9, 1999 |
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09161865 |
Sep 28, 1998 |
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5980774 |
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09161865 |
Sep 28, 1998 |
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08940936 |
Sep 30, 1997 |
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5876621 |
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Current U.S.
Class: |
252/70 ;
106/13 |
Current CPC
Class: |
C09K 3/185 20130101;
C09K 3/18 20130101 |
Class at
Publication: |
252/70 ;
106/13 |
International
Class: |
C09K 003/18 |
Claims
1. A deicing and/or anti-icing composition comprising (a) glycerol
and (b) water.
2. A deicing and anti-icing composition comprising at least 5
percent by weight of (a) plus (b) and consisting essentially of (a)
glycerol; and (b) an acid salt selected from the group consisting
of a carboxylic acid potassium salt, a hydroxycarboxylic acid
potassium salt, a dicarboxylic acid potassium salt, a carbonic acid
potassium salt and mixtures thereof; and, optionally, (c) water,
and/or (d) an effective freezing point lowering amount of a deicing
material selected from the group consisting of glycols, citrate
salts, amino acids, amino acid salts, boric acid, boric acid salts,
lignin components, gluconic acid salts, monosaccharides,
hydrocarbyl aldosides selected from the group consisting of
furanosidies, maltosides, maltotriosides, glucopyranosides,
non-alkyl glucosides and sorbitol, and mixtures thereof.
3. A composition as defined in claim 2 wherein said carboxylic acid
potassium salt comprises potassium acetate.
4. A composition as defined in claim 2 wherein said
hydroxycarboxylic acid potassium salt comprises potassium
lactate.
5. A de-icing and/or anti-icing composition comprising at least 5
percent by weight of (a) plus (b) and consisting essentially of (a)
a glycol; and (b) an acid salt selected from the group consisting
of a C.sub.1-C.sub.4 carboxylic acid salt, a C.sub.2-C.sub.4
hydroxycarboxylic acid salt, a C.sub.1-C.sub.4 dicarboxylic acid
salt, a carbonic acid salt and mixtures thereof, and, optionally,
(c) water, and/or (d) an effective freezing point lowering amount
of a deicing material selected from the group consisting of
glycerol, citrate salts, amino acids, amino acid salts, boric acid,
boric acid salts, lignin components, gluconic acid salts,
monosaccharides, hydrocarbyl aldosides selected from the group
consisting of furanosides, maltosides, maltotriosides,
glucopyranosides, non-alkyl glucosides and sorbitol, and mixtures
thereof.
6. A composition as defined in claim 5 wherein said C.sub.1-C.sub.4
carboxylic acid salt comprises potassium acetate.
7. A composition as defined in claim 5 wherein said C.sub.2-C.sub.4
hydroxycarboxylic acid salt comprises potassium lactate.
8. A deicing and/or anti-icing composition comprising at least 10
percent by weight of (a) plus (b) and consisting essentially of (a)
a glycol; and (b) at least 3 percent by weight of a carbonic acid
salt; and, optionally (c) water, and/or (d) an effective freezing
point lowering amount of a deicing material selected from the group
consisting of glycerol, citrate salts, amino acids, amino acid
salts, boric acid, boric acid salts, lignin components, gluconic
acid salts, monosaccharides, hydrocarbyl aldosides selected from
the group consisting of furanosides, maltosides, maltotriosides,
glucopyranosides, non-alkyl glucosides and sorbitol, and mixtures
thereof.
9. A composition as defined in claim 8 wherein said carbonic acid
salt comprises potassium carbonate, potassium bicarbonate, sodium
carbonate, sodium bicarbonate or a mixture thereof.
10. A method of deicing or anti-icing a surface, said method
comprising adding to a surface a deicing or ant-icing agent
comprising at least 5 percent by weight of (a) plus (b) and
consisting essentially of (a) glycerol; and (b) an acid salt
selected from the group consisting of a carboxylic acid potassium
salt, a hydroxycarboxylic acid potassium salt, a dicarboxylic acid
potassium salt, a carbonic acid potassium salt and mixtures
thereof; and, optionally, (c) water, and/or (d) an effective
freezing point lowering amount of a deicing material selected from
the group consisting of citrate salts, amino acids, amino acid
salts, boric acid, boric acid salts, lignin components, gluconic
acid salts, monosaccharides, hydrocarbyl aldosides selected from
the group consisting of furanosides, maltosides, maltotriosides,
glucopyranosides, non-alkyl glucosides and sorbitol, and mixtures
thereof.
11. A method as defined in claim 10 wherein said carboxylic acid
potassium salt comprises potassium acetate.
12. A method as defined in claim 10 wherein said hydroxycarboxylic
acid salt comprises potassium lactate.
13. A method of deicing or anti-icing a surface, said method
comprising adding to a surface a deicing or anti-icing agent
comprising at least 5 weight percent of (a) plus (b) and consisting
essentially of (a) a glycol; and (b) an acid salt selected from the
group consisting of a C.sub.1-C.sub.4 carboxylic acid salt, a
C.sub.2-C.sub.4 hydroxycarboxylic acid salt, a C.sub.1-C.sub.4
dicarboxylic acid salt, a carbonic acid salt and mixtures thereof;
and, optionally, (c) water, and/or (d) an effective freezing point
lowering amount of a deicing material selected from the group
consisting of glycerol, citrate salts, amino acids, amino acid
salts, boric acid, boric acid salts, lignin components, gluconic
acid salts, monosaccharides, hydrocarbyl aldosides selected from
the group consisting of furanosides, maltosides, maltotriosides,
glucopyranosides, non-alkyl glucosides and sorbitol, and mixtures
thereof.
14. A method as defined in claim 13 wherein said C.sub.1-C.sub.4
carboxylic acid salt comprises potassium acetate.
15. A method as defined in claim 13 wherein said C.sub.2-C.sub.4
hydroxycarboxylic acid salt comprises potassium lactate or sodium
lactate.
16. A method of deicing and/or anti-icing a surface, said method
comprising adding to a surface a deicing and/or anti-icing agent
comprising at least 10 percent by weight of (a) plus (b) and
consisting essentially of (a) a glycol; and (b) at least 3 percent
by weight of a carbonic acid salt; and, optionally, (c) water,
and/or (d) an effective freezing point lowering amount of a deicing
material selected from the group consisting of glycerol, citrate
salts, amino acids, amino acid salts, boric acid, boric acid salts,
lignin components, gluconic acid salts, monosaccharides,
hydrocarbyl aldosides selected from the group consisting of
furanosides, maltosides, maltotriosides, glucopyranosides,
non-alkyl glucosides and sorbitol, and mixtures thereof.
17. A method as defined in claim 16 wherein said acid salt
comprises a carbonic acid salt.
18. A method as defined in claim 16 wherein said carbonic acid salt
comprises potassium carbonate, sodium carbonate or a mixture
thereof.
19. A method of deicing and/or anti-icing a surface, said method
comprising adding to a said surface a deicing and/or anti-icing
agent comprising at least 5 percent by weight of (a) plus (b) and
consisting essentially of (a) a hydroxyl-containing organic
compound selected from the group consisting of hydrocarbyl
aldosides, glycols, monosaccharides, glycerol and mixtures thereof,
and (b) a carbonic acid potassium salt; and, optionally, (c) water,
and/or (d) an effective freezing point lowering amount of a deicing
material selected from the group consisting of citrate salts, amino
acids, amino acid salts, boric acid, boric acid salts, lignin
components, gluconic acid salts and mixtures thereof.
20. A method as defined in claim 19 wherein said carbonic acid
potassium salt is selected from the group consisting of potassium
carbonate, potassium bicarbonate and mixtures thereof.
21. A deicing and/or anti-icing agent comprising (a) an effective
freezing point lowering amount of a hydroxycarboxylic acid salt
selected from the group consisting of a salt of lactic acid, a salt
of glycolic acid, a salt of gluconic acid, a salt of succinic acid
and mixtures thereof.
22. An agent as defined in claim 21 wherein said hydroxycarboxylic
acid salt comprises a sodium or potassium salt of lactic acid.
23. An agent as defined in claim 21 wherein said hydroxycarboxylic
acid salt comprises a sodium or potassium salt of glycolic
acid.
24. An agent as defined in claim 21 wherein said hydroxycarboxylic
acid salt comprises a sodium or potassium salt of gluconic
acid.
25. An agent as defined in claim 21 wherein said hydroxycarboxylic
acid salt or salts are contained in or derived from an industrial
or agricultural process stream.
26. An agent as defined in claim 25 wherein said agent is prepared
by reacting at least a portion of hydroxycarboxylic acids contained
in an industrial or agricultural process stream to form
hydroxycarboxylic acid salts.
27. An agent as defined in claim 21 further comprising (b) a
effective freezing point lowering amount of a freezing point
lowering compound selected from the group consisting of carboxylic
acid salts, dicarboxylic acid salts, amino acids, salts of amino
acids, lignin components, boric acid, salts of boric acid, glycol,
glycerol, hydrocarbyl aldosides, monosaccharides and mixtures
thereof.
28. An agent as defined in claim 27 wherein said component (b)
comprises a hydrocarbyl aldoside selected from the group consisting
of furanosides, maltosides, maltotriosides, glucopyranosides,
non-alkyl glucosides, sorbitol and mixtures thereof.
29. A method of deicing and/or anti-icing a surface, said method
comprising treating said surface with a deicing and/or anti-icing
agent comprising an effective freezing point lowering amount of a
sodium or potassium salt of lactic acid.
30. A method as defined in claim 29 wherein said surface comprises
an aircraft runway, taxiway or parking area.
31. A method as defined in claim 29 wherein said deicing and/or
anti-icing agent further comprising an effective freezing point
lowering amount of a freezing point lowering compound selected from
the group consisting of glycerol, glycol, citrate salts, amino
acids, amino acid salts, boric acid, boric acid salts, lignin
components, gluconic acid salts, monosaccharides, hydrocarbyl
aldosides, carboxylic acid salts, dicarboxylic acid salts, carbonic
acid salts and mixtures thereof.
32. A method as defined in claim 29 wherein said salts of lactic
acid are contained in or derived from an industrial and/or
agricultural process stream.
33. A method as defined in claim 32 wherein said salts of lactic
acid are produced by reacting lactic acid contained in or derived
from an industrial or agricultural process stream to form
hydroxycarboxylic acid salts.
34. A method for maintaining a liquid in an unfrozen state, said
method comprising adding to said liquid an agent comprising (a) an
effective freezing point lowering amount of a compound selected
from the group consisting of hydroxycarboxylic acid esters,
hydrocarbyl aldosides and mixtures thereof, and (b) an effective
freezing point lowering amount of a freezing point lowering
additive selected from the group consisting of carboxylic acid
salts, hydroxycarboxylic acid salts, dicarboxylic acid salts,
carbonic acid salts, amino acids, amino acid salts, boric acid,
boric acid salts, ethylene glycol, propylene glycol, glycerol and
mixtures thereof.
35. A method as defined in claim 34 wherein said hydrocarbyl
aldoside is selected from the group consisting of furanosides,
maltosides, maltotriosides, glucopyranosides, non-alkyl glucosides,
sorbitol and mixtures thereof.
36. A method for transferring heat said method comprising utilizing
a heat transfer fluid prepared by a method comprising an agent
comprising (a) an effective freezing point lowering amount of a
compound selected from the group consisting of hydroxycarboxylic
acid esters, hydrocarbyl aldosides and mixtures thereof, and (b) an
effective freezing point lowering amount of a freezing point
lowering additive selected from the group consisting of carboxylic
acid salts, hydroxycarboxylic acid salts, dicarboxylic acid salts,
carbonic acid salts, amino acids, amino acid salts, boric acid,
boric acid salts, ethylene glycol, propylene glycol, glycerol and
mixtures thereof.
37. A method as defined in claim 36 wherein said hydrocarbyl
aldoside is selected from the group consisting of furanosides,
maltosides, maltotriosides, glucopyranosides, non-alkyl glucosides,
sorbitol and mixtures thereof.
38. A method for anti-icing particles, said method comprising
applying to the particle surfaces an anti-icing agent comprising
(a) an effective amount of an anti-icing agent recovered from
aircraft or airport runoff, and (b) an effective amount of an
anti-icing agent selected from the group comprising a soluble salt,
a hydrocarbyl aldoside, a monosaccharide and mixtures thereof.
39. A method as defined in claim 38 wherein said anti-icing agent
recovered from aircraft or airport runoff is selected from the
group consisting of ethylene glycol, propylene glycol, glycerol,
hydrocarbyl aldosides or mixtures thereof.
40. A method as defined in claim 38 wherein said hydrocarbyl
aldoside is selected from the group comprising furanosides,
maltosides, maltotriosides, glucopyranosides, non-alkyl glucosides,
sorbitol and mixtures thereof.
41. A method as defined in claim 38 wherein said soluble salt is
selected from the group consisting of carboxylic acid salts,
hydroxycarboxylic acid salts, dicarboxylic acid salts, carbonic
acid salts and mixtures thereof.
42. A method as defined in claim 41 wherein said carboxylic acid
salt comprises sodium acetate, potassium acetate or mixtures
thereof.
43. A method as defined in claim 41 wherein said hydroxycarboxylic
acid salt comprises sodium lactate, potassium lactate or mixtures
thereof.
44. A method as defined in claim 41 wherein said carbonic acid salt
is selected from the group comprising sodium carbonate, sodium
bicarbonate, potassium carbonate, potassium bicarbonate and
mixtures thereof.
45. A method as defined in claim 38 wherein said soluble salt is
selected from the group consisting of sodium chloride, calcium
chloride, magnesium chloride and mixtures thereof.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of application
Ser. No. 09/675,495, filed Sep. 29, 2000, now allowed, which in
turn is a continuation-in-part of application Ser. No. 09/436,811,
filed Nov. 9, 1999, now allowed, which in turn is a continuation of
application Ser. No. 09/161,865, filed Sep. 28, 1998, now U.S. Pat.
No. 5,980,774, issued Nov. 9, 1999, which in turn is a
continuation-in-part of application Ser. No. 08/940,936, filed Sep.
30, 1997, now U.S. Pat. No. 5,876,621, issued Mar. 2, 1999.
FIELD OF THE INVENTION
[0002] The present invention relates to deicing fluid compositions
and methods for deicing surfaces. More particularly the present
invention relates to deicing fluid compositions comprising
hydroxyl-containing organic compounds and/or certain organic acid
salts that are relatively environmentally benign.
BACKGROUND OF THE INVENTION
[0003] Freezing point lowering compositions are in widespread use
for a variety of purposes, especially to reduce the freezing point
of an aqueous system so that ice cannot be formed or to melt formed
ice. Generally, freezing point lowering compositions depend for
their effectiveness upon the molar freezing point lowering effect,
the number of ionic species that are made available and the degree
to which the compositions can be dispersed in the liquid phase in
which the formation of ice is to be precluded and/or ice is to be
melted.
[0004] The most pervasive of the commonly used products for deicing
are common salt, calcium chloride and urea, with common salt
(sodium chloride) being the least expensive and most commonly used.
Common salt is widely used to melt ice on road surfaces and the
like. In this manner the salt forms a solution with the available
liquid in contact with the ice and thereby forms a solution with a
lower freezing point than the ice itself so that the ice is melted.
Chloride salts however suffer from relatively severe drawbacks,
such as the harmful effects on surrounding vegetation by preventing
water absorption in the root systems, the corrosive effects on
animal skin such as the feet of animals, clothing, roadways and
motor vehicles, and the deleterious effects on surface and ground
water. Thus, any new method of deicing or new deicing composition
that can reduce the amount of chloride salts would solve a long
felt need in the art.
[0005] For example, in roadway deicing applications, liquid calcium
chloride (32%) is typically the preferred material when
temperatures are too low for rock salt to be effective. However,
the use of chloride salts often is not permitted or needs to be
reduced in certain areas because of its highly corrosive nature,
which causes destruction of surrounding vegetation, damage to
roadways and vehicles, and contamination of water supplies.
[0006] Another drawback of certain prior art deicing fluids is the
high chemical and biological oxygen demand that make them
environmentally unfavorable. The glycols are exemplary of deicing
fluids that particularly suffer from this type of environmental
drawback. Thus, any new method of deicing or new deicing
composition that can reduce the amount of glycols would solve a
long felt need in the art.
[0007] Due to the problems associated with deicing agents as
described above, there have been attempts to prepare even more
deicing agents. For, example, Kaes, U.S. Pat. No. 4,448,702,
discloses the use of a freezing-point lowering composition and
method that calls for the addition of a water-soluble salt of at
least one dicarboxylic acid having at least three carbon atoms,
such as a sodium, potassium, ammonium or organoamine salt of
adipic, glutaric, succinic or malonic acid.
[0008] Peel, U.S. Pat. No. 4,746,449, teaches the preparation of a
deicing agent comprising 12-75% acetate salts, trace-36% carbonate
salts, 1-24% formate salts and 1-32% pseudolactate salts that is
prepared from a pulp mill black liquor by fractionating the black
liquor into a low molecular weight fraction and concentrating the
collected low molecular weight fraction to produce the deicing
agent.
[0009] U.S. Pat. No. 4,960,531 teaches that small amounts of methyl
glucosides, i.e., less than 10%, in combination with a low amount,
i.e., about 2.5%, of potassium carbonate can be employed as a
trigger to conventional salt deicers. The '531 patent is an
improvement patent on United States Reissue Pat. No. RE 32,477 that
teaches the use of a salt mixture of sodium and potassium chloride
and an amide. Other inorganic salts are also known to be useful as
freezing point lowering agents such as magnesium chloride,
potassium phosphates, sodium phosphates, ammonium phosphates,
ammonium nitrates, alkaline earth nitrates, magnesium nitrate,
ammonium sulfate, and alkali sulfates.
[0010] Special mention is also made of Sapienza, U.S. Pat. No.
5,876,621 and Sapienza, U.S. Pat. No. 5,980,774 that disclose
especially useful deicing and anti-icing compositions.
[0011] Solutions of low freezing point deicing and anti-icing
agents typically include brines, ethylene glycol and propylene
glycol solutions. The use of brines in anti-icing compounds can
reduce, although not eliminate, the impacts of chlorides. Brines
are used to transfer heat at temperatures below the normal freezing
point of water. Ethylene glycol solutions are well known for use as
coolants for automobiles and the like in regions in which the
temperature may fall below the normal freezing point of water.
Ethylene and propylene glycols are used in relatively large
quantities at major airports in northern climates in order to keep
air traffic flowing during inclement weather. The fluids generally
are applied to the wings, fuselage and tail of aircraft as well as
the runways to remove ice. However, these glycol compounds likewise
have environmental drawbacks and can be detrimental to sewage
treatment processes.
[0012] Other prior art deicing fluids, such as alcohols, have toxic
effects and high volatility particularly in the low molecular
weight range and may be the cause of offensive smell and fire
danger. Furthermore, mono- and polyhydric alcohols oxidize in the
presence of atmospheric oxygen to form acids, which can increase
corrosion of materials.
[0013] Yet another reason why new deicing fluids are needed emerges
from the recent changes to the freezing point requirements of the
SAE AMS 1435A specification for airport runway deicing fluids.
Newer AMS 1435A specifications require deicing fluids to have a
freezing point of less than -14.5.degree. C. for a 1:1 weight
dilution. These specifications are such that many technologies,
including existing glycol-based fluids currently used commercially,
no longer meet the new requirements, including ASTM D 1177.
[0014] As such there exists in the art a need for new and improved
deicing and/or anti-icing agents. Preferably these are free or
substantially free of inorganic salts, are environmentally benign
and are prepared from relatively inexpensive raw materials while
still possessing desirable freezing point depression properties.
Likewise, there also exists a need in the art for new deicing
and/or anti-icing agents that can be used in combination with prior
art deicing agents, such as inorganic salts or glycols, to
substantially reduce the amount of inorganic salts or glycols, and
thereby concomitantly reduce the environmental affects of the salts
and/or glycols. Surprisingly, it has been found that compositions
disclosed herein meet these needs.
[0015] The total active composition of the new deicing and/or
anti-icing agents can vary from about 5 to about 100 weight
percent. Improved solid deicers can be prepared that can be applied
in the same manner as solid chloride salts with the environmental
advantages described earlier.
SUMMARY OF THE INVENTION
[0016] Accordingly, in one preferred embodiment the present
invention provides a deicing and/or anti-icing composition
comprising (a) glycerols and (b) water.
[0017] In another preferred embodiment the present invention also
provides a method for de-icing or anti-icing a surface comprising
applying to the surface an effective amount of a de-icing agent
and/or anti-icing agent comprising glycerols and water.
[0018] In a further preferred embodiment of the present invention
there is provided a deicing and/or anti-icing composition
comprising (a) glycerol, (b) an organic acid salt selected from the
group consisting of a carboxylic acid salt, a hydroxycarboxylic
acid salt, a dicarboxylic acid salt and mixtures of any of the
foregoing and (c) water.
[0019] In still a further preferred embodiment of the present
invention there is provided a method for de-icing or anti-icing a
surface comprising applying to the surface an effective amount of a
de-icing agent and/or anti-icing agent comprising (a) glycerols,
(b) an organic acid salt selected from the group consisting of a
carboxylic acid salt, a hydroxycarboxylic acid salt, a dicarboxylic
acid salt and mixtures of any of the foregoing and (c) water.
[0020] In another further preferred embodiment of the present
invention there is provided a deicing and/or anti-icing composition
comprising (a) a hydroxyl-containing organic compound selected from
the group consisting of hydrocarbyl aldosides including di- and
polysaccharides such as sucrose, sorbitol and other hydrogenation
products of sugars, monosaccharides, maltodextrins and sucrose,
maltitol, glycols, monosaccharides, glycerol and mixtures of any of
the foregoing, (b) a carbonate salt and (c) water.
[0021] In still another further preferred embodiment of the present
invention there is provided a method for de-icing and/or anti-icing
a surface comprising applying to the surface an effective amount of
a de-icing agent and/or anti-icing agent comprising (a) a
hydroxyl-containing organic compound selected from the group
consisting of hydrocarbyl aldosides including di- and
polysaccharides such as sucrose, sorbitol and other hydrogenation
products of sugars, monosaccharides, maltodextrins and sucrose,
maltitol, glycols, monosaccharides, glycerol and mixtures of any of
the foregoing, (b) a carbonate salt and (c) water.
[0022] It is still further contemplated that useful deicing and/or
anti-icing agents can be prepared from combinations of sorbitol and
glycerol with water and with other materials such as carbonates and
acetates, etc. These are especially useful for aircraft and airport
runway deicing and/or anti-icing applications.
[0023] The present inventors have still further found that
excellent deicing compositions can be obtained by upgrading
recovered airport and/or aircraft runoffs or other sources of
recycled or recovered glycols (i.e., radiator fluids and gas
dehydration glycol fluid). For example, the recovered runoffs,
which typically contain at least about 5%, preferably at least
about 10% by weight of glycol, or more, can be upgraded by adding
effective amounts of (a) a hydroxyl-containing organic compound
selected from the group consisting of hydrocarbyl aldosides,
sorbitol and other hydrogenation products of sugars,
monosaccharides, maltodextrins and sucrose, maltitol, glycols,
monosaccharides, glycerols and mixtures thereof and/or (b) an
organic acid salt selected from the group consisting of a carbonic
acid salt, a carboxylic acid salt, a hydroxycarboxylic acid salt, a
dicarboxylic acid salt and mixtures thereof. These upgraded runoffs
can then be used directly as de-icing and/or anti-icing agents for
surfaces such as bridges, runways and highways. Additionally, these
can be used for the deicing or anti-icing of almost any surface,
including, but not limited to particulate surfaces, such as salt,
mineral ores and/or coal piles.
[0024] Another benefit of the present invention is seen in that
when carbohydrates are added to salts, such as potassium acetate,
the viscosity and wetting abilities of the deicing and/or
anti-icing compound are increased. This has a dual effect of
providing a compound that will not readily run off the surface, and
of also providing a more persistent film that does not leave a dry
powder after the surface later dries.
[0025] Further, in embodiments where some inorganic salt can be
tolerated, such as on certain highway applications, the present
invention further provides for upgrading recovered airport runoffs
by addition of effective amounts of inorganic salts, such as sodium
chloride, magnesium and/or calcium chloride and the like. Such
compositions have improved environmental effects by reducing the
amount of inorganic salts employed to obtain the same or better
deicing and/or anti-icing properties.
[0026] The present invention still further provides a method for
reducing the amount of inorganic salt necessary to achieve
effective deicing and/or anti-icing, comprising adding to the
inorganic salt, an effective amount of a deicing agent selected
from the group consisting of glucosides, furanosides, maltosides,
maltotriosides, glucopyranosides, sorbitols and other hydrogenation
products of sugars, monosaccharides, maltodextrins and sucrose,
glycerols and mixtures of any of the foregoing.
[0027] The compositions and methods of the present invention can be
applied to a wide variety of surfaces, including both metallic and
non-metallic surfaces of aircraft, which prevents icing, removes
frozen water from the surface and prevents its reformation. The
invention provides for a deicing composition that can be used on
airplanes, runways, bridges, streets and the like. Further, the
compositions can be used in heat transfer applications and other
applications in which it is preferable to maintain a liquid in the
unfrozen state, e.g., as in a fire extinguisher, car radiators,
heat transfer systems, gas dehydration systems, lavatory fluids,
protection of plumbing lines, drilling fluids, etc. In these
applications, the compositions of the present invention can be use
to replace completely or partially, or in addition to any of the
glycols normally employed, including, triethylene glycol.
Additionally, the present invention provides for an anti-icing
composition that can be applied to a surface, such as bridges,
prior to the onset of icing conditions in order to prevent icing
from occurring. Still further, the compositions of the present
invention can be used as a deicer and/or anti-icer for pre-harvest
fruits, vegetable crops and other vegetation, such as golf course
greens.
[0028] In still further embodiments, the compositions of the
present invention are useful to prevent freezing or de-freezing in
a wide variety of other applications. An example is that the
compositions of the present invention can be used in drilling
fluids used to break-up (melt) frozen gas hydrates.
[0029] In another embodiment of the present invention, there is
provided a method of producing deicing and/or anti-icing
formulations using recovered airport storm water as a medium for
producing organic salts such as potassium acetate and potassium
lactate in order to provide a glycol/organic acid salt deicing
formulation.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0030] The present invention provides novel compositions useful as
deicing agents and/or anti-icing agents. The deicing agents of the
present invention comprise certain hydroxyl-containing organic
compounds, certain organic acid salts, alone or in admixture with
each other.
[0031] 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.
[0032] The amount of deicing or anti-icing agent of the present
invention that is present in the total composition of the present
invention can vary from about 5 to about 100 weight percent.
Preferably, the de-icing agent and/or anti-icing agent is present
in an amount ranging from about 5 or 10 to about 90 weight percent,
more preferably is present in an amount ranging from about 15 to
about 80 weight percent, and most preferably is present in an
amount ranging from about 30 to about 70 weight percent. In many
preferred embodiments, the deicing agents and/or anti-icing agents
are used in about the same proportion as water, i.e., in a weight
ratio of about 1:1 agent:water. In solid formulations, the deicing
and/or anti-icing agents may comprise 100% of the final
formulation.
[0033] The hydroxyl-containing organic compounds useful in certain
embodiments of the present invention are generally selected from
the group of hydrocarbyl aldosides, sorbitol and other
hydrogenation products of sugars, monosaccharides, maltodextrins
and sucrose, maltitol, glycols, monosaccharides, glycerols and
mixtures thereof.
[0034] The hydrocarbyl aldosides useful in the practice of the
present invention are known to those of ordinary skill in the art,
such as the di- and polysaccharides. An example of a hydrocarbyl
aldoside is the glucopyranoside sucrose (table sugar). Preferably,
the hydrocarbyl aldosides comprise alkyl aldosides. Alkyl aldosides
can be prepared, for example, as described in U.S. Pat. Nos.
4,223,129 and 4,329,449 that are incorporated herein by
reference.
[0035] Typical of the alkyl aldosides useful in the practice of the
present invention are alkyl furanosides, alkyl maltosides, alkyl
maltotriosides, alkylglucopyranosides mixtures thereof and the
like.
[0036] Other hydroxyl-containing organic compounds useful in the
practice of the present invention are sorbitol and other
hydrogenation products of sugars, monosaccharides, maltodextrins
and sucrose, such as maltitol, xylitol and mannitol, glycols such
as ethylene glycol and propylene glycol, glycerols and
monosaccharides and mixtures of any of the foregoing. These
materials are available commercially and are well known to those of
ordinary skill in the art.
[0037] The organic salt components useful in the practice of the
present invention include the carboxylic acid salts, the
hydroxycarboxylic acid salts, dicarboxylic acid salts and mixtures
thereof.
[0038] The carboxylic acid salts that are useful in the practice of
the present invention are likewise available commercially and are
known to those skilled in the art. Carboxylic acid salts preferred
for use in the practice of the present invention comprise the
sodium or potassium salts of formates, acetates, propionates,
butyrates and mixtures thereof. Also preferred are potassium
acetate and/or potassium formate.
[0039] The hydroxycarboxylic acid salts that are useful in
accordance with the present invention are available commercially
and are known to those skilled in the art. Preferred
hydroxycarboxylic acid salts comprise the salts of lactic acid,
such as sodium lactate and potassium lactate. However, any of the
cesium, sodium, potassium, calcium and/or magnesium salts of
hydroxycarboxylic acids may be employed such as sodium
gluconate.
[0040] The dicarboxylic acid salts that are useful in accordance
with the present invention are available commercially and are known
to those skilled in the art. Preferred dicarboxylic acid salts
comprise sodium and potassium salts of oxalates, malonates,
succinates, glutarates, adipates, maleates, fumarates and mixtures
of any of the foregoing.
[0041] Also useful as a deicing component in certain of the
compositions of the present invention are the high solubility
carbonic acid salts. Preferred carbonate salts for use in the
practice of the present invention are potassium carbonate,
potassium bicarbonate, sodium carbonate and cesium carbonate.
Potassium carbonate is especially preferred. In many applications,
the addition of carbonic acid salts, such as potassium carbonate,
has been found to provide synergistically unexpected reductions in
freezing points. For example, a 50/50 mixture of potassium acetate
and water has a freezing point of -60.degree. C., as seen in Table
1, Example 9. When this solution is mixed with the 50/50 sorbitol
water mixture from Table 1, Example 1 (freezing point -11.degree.
C.) the resulting soludion as reported in Example 23 has a freezing
point of -32.degree. C., which is only 60.degree. C. below the
arithmetic average of the two base stocks. However, it was
discovered that when combining potassium carbonate solution from
Example 7 (47% potassium carbonate in water, freezing point
-20.degree. C.) on a 1:1 basis with the 50/50 sorbitol/water
mixture from Example 1 (freezing point -11.degree. C.), the
resulting compound as reported in Example 11 had the surprisingly
low freezing point of -27.degree. C., which is 15.5.degree. C.
lower than the arithmetic average.
[0042] In certain instances, where the pH of the carbonic acid or
its salt is too high to meet regulatory or industry specifications,
it is contemplated herein to use a buffering agent to lower the pH
to acceptable levels. Suitable buffering agents may be selected
from any of the known buffering agents. Especially preferred is
boric acid. For example, in highway applications, compositions
including potassium carbonate and/or potassium bicarbonate in
combination with a hydroxyl-containing component of the present
invention or industrial process stream containing same, the pH in
some formulation may be above 12, and most state highway
departments prefer deicers having a pH below 12. An effective
amount of boric acid or other buffering agent may be added to
reduce the pH of the deicing compounds to less than 12, i.e., from
about 11.5 to about 11.8 or lower, to meet the specifications.
Alternatively, during the preparation of the carbonate, the pH can
be adjusted by continued reaction to bicarbonate or separate
addition of same.
[0043] Thus, the instant invention provides equally effective, but
considerably less expensive product than the prior art, as
potassium carbonate of the present invention costs generally about
30% less than the commonly used potassium acetate of the prior art.
Carbonic acid salts are available commercially and can be prepared
by methods known to those of ordinary skill in the art.
[0044] Generally the organic freezing point lowering agents useful
in the practice of the present invention may be used in solid form
or mixed with water as pure components. However, it is contemplated
that the present invention may employ a number of industrial or
agricultural process streams that comprise a water soluble solution
of carboxylic acid salts, hydroxycarboxylic acid salts and/or
dicarboxylic acid salts. Although the purification of these
materials is difficult due to their similarity in solubility
characteristics to water, the dilute industrial or agricultural
streams may be used directly in the practice of the present
invention. The present invention contemplates, for non-limiting
examples, the use of industrial or agricultural process streams
selected from the group consisting of a grain stillage (grain
steepwaters), a wood stillage, agricultural or milk fermentation
processes, sugar extraction processes such a desugared sugar beet
molasses and/or desugared sugar cane molasses, hydrogenation
products of sugars, monosaccharides, maltodextrins and sucrose and
mixtures of any of the foregoing. Generally, the components of the
present invention are present in or may be readily derived by
alcoholysis of the industrial process streams.
[0045] Certain of these industrial process streams may include
components such as low molecular weight sugars, such as, for
example, sorbitols, sucroses, maltoses and glucoses. Where desired,
by subjecting these waste streams to alcoholysis (with an alkyl
alcohol) under conditions such as reacting with an alkyl alcohol in
the presence of a cation exchange material or other acid, or the
addition of an alkyl alcohol to a heated fermentation liquor at
least some of the sugars will be converted to glucosides. For
instance, ethanol treatment of a typical agricultural fermentation
process stream comprising glucose would be at least partially
converted to ethyl glucoside.
[0046] In addition to (a) the certain hydroxyl-containing organic
compounds and (b) the certain organic acid salts, it is
contemplated by the present invention that other organic components
may be included in the deicing and/or anti-icing compositions of
the present invention. Exemplary of such materials are citrate
salts such as sodium citrate, amino acids and their salts such as
lysine glutamate, sodium pyrrolidone carboxylate and sodium
glucoheptonate; lignin components such as lignin sulfonate; boric
acid and its salts; sodium gluconate and other gluconic acid salts;
and mixtures of any of the foregoing.
[0047] 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, or spreading for
solid forms onto the surface desired to be treated. In the case of
deicing, the surface already has ice formed thereon or liquid is
already in ice form, and the deicing compositions of the present
invention melt the ice already formed and are further effective in
preventing additional ice formation. In the case of anti-icing,
upon learning of a weather forecast that predicts possible
dangerous icing conditions, the roads, bridges, airplanes, runways,
growing produce or other surfaces or liquids can be pretreated with
the anti-icing compositions of the present invention in similar
manner in order to prevent ice formation on the treated surfaces or
in the treated liquids.
[0048] 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
agents of methyl glucoside; a mixture of sorbitol and glycerol; or
a mixture of methyl glucoside, sorbitol and/or glycerol with sodium
lactate and/or potassium lactate.
[0049] For the deicing and/or anti-icing of runways, it is
preferred 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; a mixture of sodium lactate and/or potassium lactate with
potassium acetate; or potassium carbonate.
[0050] For de-icing and/or anti-icing of pre-harvest fruits and
vegetables, such as fruit trees or grape vines, it is preferred to
use de-icing and/or anti-icing agents of a hydroxyl-containing
organic compound in combination with an organic acid salt,
particularly a lactate salt.
[0051] The present invention also provides for the re-use of
glycols recovered from airport collection systems for the de-icing
and/or anti-icing of bridges, runways and highways. Of course,
glycols can be recovered or recycled from other sources, such as,
but not limited to, radiator fluids and/or gas dehydration glycol
fluids. Currently, pure glycols are used to de-ice and/or anti-ice
aircraft. The practice of collecting the glycol solutions that run
off aircraft, either by using dedicated drainage systems or vacuum
collection trucks, is increasing. However, the runway material
cannot be collected efficiently and the salvaged material is very
dilute. The present inventors have found that the used glycols can
be recovered and reused as de-icing agents and/or anti-icing agents
by upgrading these glycols and then re-applying the upgraded
glycols. The upgrading of these glycols comprises the addition of a
polyhydroxyl and/or organic acid salt to the recovered glycol.
Also, where tolerable, the recovered glycols can be upgraded by the
addition of inorganic salts, such as sodium chloride. The
formulations of the present invention, such as sorbitol/glycerol or
methyl glucoside can be recovered in the same way.
[0052] Generally, after application on the runway, the glycols are
recovered in concentrations of about 10-20 weight percent. In
accordance with the present invention, the addition of from about 5
to about 50 weight percent, preferably from about 30 to about 40
weight percent, based on the total weight of the composition, of
the hydroxyl-containing organic compounds of the present invention,
the organic acid salts of the present invention or combinations
thereof provides for an effective upgraded glycol-recovered runoff,
which can be reused for de-icing and/or anti-icing on bridges, for
airport or aircraft deicing and highways. Where inorganic salts can
be tolerated, similar amounts of inorganic salts alone, or in
combination with the hydroxyl-containing organic compounds and/or
organic acid salts, may also be added.
[0053] In other situations where some inorganic salts can be
tolerated, the present invention provides an improved method for
reducing the amount of salt to be added to achieve an equivalent or
better deicing and/or anti-icing effect, and thereby reduce the
detriment to the environment. In these embodiments, the present
invention provides for replacing a portion of the inorganic salt
with the hydroxyl-containing organic compounds of the present
invention, the organic acid salts of the present invention, or a
combination thereof.
[0054] The present invention also provides an advantageous method
for producing deicing and/or anti-icing formulations using
recovered airport storm water as a medium for production of organic
salts, such as potassium acetate and potassium lactate, in order to
accomplish a glycol/organic acid salt deicing formulation. This
advantageous method addresses two issues: (1) the fact that the
concentration of glycol or other deicing component recovered in
storm water is usually quite low--about 10% or less; and (2)
transportation of contained water as a major cost item in liquid
deicing formulations. Technologies to concentrate the storm water
are available, but the cost increases substantially as a function
of the level of glycol concentration required.
[0055] Typically organic salts, such as potassium acetate, are
produced by adding glacial acetic acid to a solution of potassium
hydroxide. In the method of the present invention, the KOH solution
would be prepared at or near the airport by adding solid KOH to
recovered storm water containing glycol instead of water. Glacial
acetic acid would then be added to produce the organic salt.
[0056] Since the airports are generally located at or near
metropolitan centers, this method would produce the product near
its point of consumption, reducing the cost of transportation.
Further, by using storm water instead of water to produce the final
formulation, a lower concentration of glycol is needed to achieve
the desired final concentration.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0057] The testing results as reported in the examples below were
obtained using the following procedures. Freezing points were
determined by the ASTM D 1177 method. A fluid sample was placed in
a cold bath and cooled at a steady rate while monitoring the
temperature of the sample and plotting temperature as a function of
time. When ice crystals begin to form in a sample, the temperature
remains constant until the entire sample freezes, creating an
inflection point on the cooling curve indicative of the fluid
freezing point. This test is useful in determining the useable
temperature range of a deicing fluid and provides an indication as
to the ice melting capability and dilution capacity of the
fluid.
[0058] The Kinematic Viscosity of the fluid was determined by the
ASTM D445 method and is defined as a fluid's resistance to flow.
Viscosity is an important property of any fluid, and in the case of
deicing fluids, viscosity is important in aspects of fluid
application and adherence. A fluid with a very high viscosity may
be too thick to spray through application equipment, whereas a
fluid with a very low viscosity may be too thin to adhere to the
treated surface and run off. An optimum viscosity permits a fluid
to be applied easily with conventional spray equipment and allows
it to adhere to the surface for extended periods of time to prevent
ice from forming on and bonding to the surface.
[0059] Conductivity is a measure of a fluid's ability or tendency
to conduct an electric current. This property is an important
factor in determining if a fluid is acceptable to be used near
electrical wiring. Additionally, high conductivity can also lead to
corrosion of metals, as corrosion is an electrochemical
reaction.
[0060] The pH of a fluid may affect its compatibility with various
materials of construction it may contact (metals in particular). In
order to minimize metal corrosion, most deicing fluids are
formulated to a pH that is neutral to slightly basic in order to
keep the fluid within the passivation range of the metals commonly
used in construction.
[0061] COD and BOD were measured by standard EPA methods. COD is
defined as the amount of oxygen required to chemically oxidize an
organic compound completely to carbon dioxide and water. It is
expressed as grams O.sub.2 per gram of compound. BOD is defined as
the amount of oxygen consumed through the biodegradation of an
organic compound by the action of microorganisms. The BOD/COD ratio
often provides useful information as to the biodegradability and
rate of biodegradation of an organic compound. Compounds that
exhibit a high BOD or a high BOD/COD ratio, such as propylene
glycol, can lead to rapid depletion of dissolved oxygen in water,
which can lead to fish kills in natural waterways. This is a
potential hazard for deicing fluid run off into storm sewers and
streams. Ideally, a deicing fluid should biodegrade completely, but
at a moderate rate that is less than that of propylene glycol.
[0062] The DOT corrosion test method used follows the NACE Standard
TM-01-69 (1976 revision) as modified by Pacific Northwest
Snowfighters consortium. This test is applicable to roadway deicing
chemicals that are likely to contact carbon steel structural
materials used in application equipment, automobiles, bridges, etc.
It is intended to simulate accelerated conditions of repeated and
prolonged exposures of steel substrates to dilute concentrations of
deicing chemicals under cyclic wet-dry conditions. Deicing
chemicals were evaluated for rate of corrosion of standard carbon
steel substrate and compared with the rates obtained for distilled
water and 3% sodium chloride solutions as controls.
[0063] The following examples are provided for illustrative
purposes and are not to be construed to limit the scope of the
claims in any manner whatsoever.
EXAMPLES 1-34
[0064] Deicing and/or anti-icing fluids were prepared from pure
compounds in accordance with the present invention. They were then
tested for freezing point, viscosity, conductivity, pH, COD, BOD
and corrosion. MBS refers to desugared beet molasses from Michigan
Beet Sugar. The results are reported below in Table 1.
1 EXAMPLE 1 2 3 4 5 6 7 8 9 10 11 12 13 Composition Sorbitol 50 0 0
0 0 0 0 0 0 0 25 0 0 MeG 0 50 0 0 0 0 0 0 0 0 0 25 0 Glycerol 0 0
50 0 0 0 0 0 0 0 0 0 25 Propylene Glycol 0 0 0 50 0 0 0 0 0 0 0 0 0
MBS 0 0 0 0 50 0 0 0 0 0 0 0 0 Sucrose 0 0 0 0 0 50 0 0 0 0 0 0 0
Potassium Carbonate 0 0 0 0 0 0 47 0 0 0 25 25 25 Sodium Formate 0
0 0 0 0 0 0 25 0 0 0 0 0 Potassium Acetate 0 0 0 0 0 0 0 0 50 0 0 0
0 Sodium Lactate 0 0 0 0 0 0 0 0 0 50 0 0 0 Water 50 50 50 50 50 50
53 75 50 50 50 50 50 Properties Freezing Point, .degree. C. -11 -16
-23 -33 -16 -7.5 -20 -19.5 -60 -32 -27 -33 -37 Viscosity, cSt
22.degree. C. 7.6 8.4 4.5 6.0 4.9 10.4 4.3 1.9 3.8 16.9 8.4 9.5 7.2
-7.degree. C. 39.4 40.4 15.8 26.3 15.0 44.7 11.5 4.5 10.2 110.3
27.5 32.4 19.8 Conductivity, mS/cm 0.003 0.668 0.003 0.002 294
<.001 880 354 654 401 466 486 470 pH 5.48 4.53 5.04 5.81 8.66
5.88 >13 7.91 9.87 7.19 12.63 12.73 12.72 COD kg/kg 0.60 0.63
0.68 0.82 0.32 0.53 0.04 0.04 0.34 0.47 0.21 0.26 0.26 BOD kg/kg
0.34 0.34 0.33 0.53 0.13 0.24 <0.005 0.33 0.18 0.24 0.16 0.10
0.18 PNSDOT Corrosion -3.1 -0.8 -3.5 -2.2 14.9 -2.58 0.3 68.2 -2.5
-1.8 -1.1 -0.5 -5.5 EXAMPLE 14 15 16 17 18 19 20 21 22 23 24 25 26
Composition Sorbitol 0 0 0 25 0 0 0 0 0 25 0 0 0 MeG 0 0 0 0 25 0 0
0 0 0 25 0 0 Glycerol 0 0 0 0 0 25 0 0 0 0 0 25 0 Propylene Glycol
25 0 0 0 0 0 25 0 0 0 0 0 25 MBS 0 25 0 0 0 0 0 25 0 0 0 0 0
Sucrose 0 0 25 0 0 0 0 0 25 0 0 0 0 Potassium Carbonate 25 25 25 0
0 0 0 0 0 0 0 0 0 Sodium Formate 0 0 0 25 25 25 25 25 25 0 0 0 0
Potassium Acetate 0 0 0 0 0 50 0 0 0 25 25 25 25 Sodium Lactate 0 0
0 0 0 0 50 0 0 0 0 0 0 Water 50 50 50 53 75 50 50 50 50 50 50 50 50
Properties Freezing Point, .degree. C. -52* -36 -26 -22 -23 -34 -15
-21 -24 -32 -34 -41 -51.3 Viscosity, cSt 22.degree. C. 6.7 6.5 10.3
9.2 9.2 6.4 6.9 6.3 9.6 5.7 6.3 4.4 4.7 -7.degree. C. 22.1 16.1
33.9 32.9 71.9 23.5 27.3 22.0 38.4 18.3 21.2 13.6 16.1
Conductivity, mS/cm 476 532 444 424 377 414 391 471 426 300 322 287
274 pH 13.21 12.13 12.32 7.71 7.63 7.62 8.11 8.21 7.76 8.87 8.90
8.88 9.33 COD kg/kg 0.35 0.08 0.22 0.28 0.37 0.31 0.42 0.18 0.31
0.43 0.47 0.44 0.59 BOD kg/kg 0.19 0.08 0.14 0.20 0.15 0.16 0.24
0.13 0.24 0.24 0.14 0.32 0.35 PNSDOT Corrosion -6.4 -1.2 -6.6 13.8
77.4 28.0 43.5 41.5 -2.5 -2.6 -2.5 -2.6 -2.6 EXAMPLE 27 28 29 30 31
32 33 34 Composition Sorbitol 0 0 25 0 0 0 0 0 MeG 0 0 0 25 0 0 0 0
Glycerol 0 0 0 0 25 0 0 0 Propylene Glycol 0 0 0 0 0 25 0 0 MBS 25
0 0 0 0 0 25 0 Sucrose 0 25 0 0 0 0 0 25 Potassium Carbonate 0 0 0
0 0 0 0 0 Sodium Formate 0 0 0 0 0 0 0 0 Potassium Acetate 25 25 0
0 0 0 0 0 Sodium Lactate 0 0 25 25 25 25 25 25 Water 53 75 50 50 50
50 50 50 Properties Freezing Point, .degree. C. -40 -31 -27 -29 -39
-44.3* -29 -27 Viscosity, cSt 22.degree. C. 4.3 6.4 10.9 10.9 8.2
8.1 8.3 13.4 -7.degree. C. 12.9 21.7 59.2 60.1 36.3 40.3 36.1 71.6
Conductivity, mS/cm 355 292 199 202 200 181 276 189 pH 8.83 8.87
7.61 7.60 7.51 7.90 8.32 7.55 COD kg/kg 0.33 0.42 0.49 0.53 0.54
0.61 0.37 0.48 BOD kg/kg 0.20 0.29 0.34 0.33 0.36 0.40 0.25 0.25
PNSDOT Corrosion 18.0 -2.4 -1.3 -1.5 -1.2 -0.7 -0.8 -0.3
EXAMPLES 35-38
[0065] Deicing and/or anti-icing compositions prepared in
accordance with the present invention employing industrial or
agricultural streams as at least part of the deicing and/or
anti-icing composition were tested for freezing points. The results
are set forth in Table 2.
2 TABLE 2 Example 35 36 37 38 Composition CSB 25 0 25 0 Potassium
Carbonate 25 25 0 0 CMS 0 25 0 25 Potassium acetate 0 0 25 25 Water
50 50 50 50 Properties Freezing Point, .degree. C. -44 -38 -48
-42
[0066] CSB refers to Molasses Concentrated Separator Bottoms from
Idaho Beet Sugar (Amalgamated Sugar) having the following
approximate composition:
3 % ON DRY COMPONENT GROUPS % BY WEIGHT SUBSTANCE Dissolved Solids
(RDS) 74.84 -- Ash 22.81 30.47 Crude Protein 19.44 25.97 Nitrogen
Compounds (As N) 3.11 4.16 .alpha.-Amino Nitrogen 0.41 0.55
Compounds (As N) INDIVIDUAL COMPOUNDS Sucrose 13.13 17.54 Raffinose
3.96 5.29 Invert 0.020 0.027 Betaine 8.95 11.82 Potassium 8.85
11.82 Sodium 1.98 2.65 Calcium 0.04 0.05 Chloride 1.83 2.44 Nitrate
0.70 0.94 Sulfate 2.1 2.8 Pyrrolidone Carboxylic Acid (PCA) 6.29
8.40 Tyrosine 0.28 0.38 Serine 0.05 0.07 Isoleucine and/or Proline
0.47 0.63 Glutamic Acid 0.88 1.18 Aspartic Acid 0.89 1.19 Threonine
0.015 0.02 Alanine 0.16 0.21 Valine 0.12 0.16 Glycine 0.06 0.08
[0067] CMS refers to Concentrated Molassess Solids from Michigan
Beet Sugar (Monitor Sugar) having the following approximate
composition (DS=dry solids):
4 Total Solids (Brix) 70% approx. Sucrose 26.5% on DS approx.
Raffinose 5.0% on DS approx. Nitrogen Compound (as N) 3.5% on DS
approx. Crude Protein 22.0% on DS approx. Betaine 8.5% on DS
approx. Amino Acids 0.5% on DS approx. Ash 30.0% on DS approx. Bulk
Density 11.2 lbs./gallon approx. Others 4.0% on DS approx.
EXAMPLE 39
[0068] A mixture of 25% by weight water, 65% by weight ethyl
lactate and 10% by weight sodium lactate was prepared. No crystal
formation was observed at a temperature of -50.degree. C.
EXAMPLE 40
[0069] A mixture of 50% by weight water and 50% by weight ethyl
lactate was prepared. The mixture had a melting point of
-18.degree. C.
EXAMPLE 41
[0070] A mixture of 70% by weight water, 24% by weight ethyl
lactate and 6% by weight sodium lactate was prepared. The mixture
had a melting point of -25.degree. C. as determined by DSC and a pH
of 6.0. For comparison, a 70% by weight water/30% by weight
ethylene glycol solution has a melting point of -18.degree. C.
EXAMPLE 42
[0071] The addition of 50% by weight of a 50% mixture of ethyl
lactate in water to a concentrated, filtered corn steep liquor
(containing 50% water and 50% solids comprising mostly lactic acid
and sugars) caused a reduction in freezing point from -11.degree.
C. to -16.degree. C. The addition of 2% by weight sodium lactate
further reduced the freezing point to -20.degree. C.
EXAMPLE 43
[0072] A mixture of 60% by weight water, 20% by weight sodium
lactate, 2% by weight proline (an amino acid), 8% by weight
sorbitol and 10% by weight sodium pyrrolidone carboxylate (sodium
PCA) was prepared. No crystal formation at -35.degree. C. was
observed. The pH was 6.57. For comparison a 50% by weight solution
propylene glycol has a freezing point of -36.degree. C.
EXAMPLE 44
[0073] A mixture of 12% by weight methyl lactate, 44% by weight
methyl glucoside and 44% by weight water was prepared. A melting
point of -18.degree. C. was observed. The mixture had a pH of
5.
EXAMPLE 45
[0074] A mixture containing 35% by weight methyl lactate, 35% by
weight methyl glucoside and 30% by weight water has a melting point
of -21.degree. C. as determined by DSC.
EXAMPLE 46
[0075] A filtered concentrated liquid residue of a 50% mixture of
corn stillage and steepwater containing 50% by weight water with a
freezing point of -12.degree. C. is heated to 90.degree. C. and
treated with 5% ethanol for 8 hours. The resulting mixture has a
freezing point of -17.degree. C. The addition of 2% sodium lactate
further reduces the freezing point to -21.degree. C.
EXAMPLES 47-53
[0076] Additional deicing and anti-icing fluids containing
potassium carbonate were prepared in accordance with the present
invention. The results are set forth below in Table 3.
5TABLE 3 Example 47 48 49 50 51 52 53 Composition Methyl Glucoside
10 10 0 0 0 15 0 Sodium Lactate 10 0 0 0 10 0 0 Potassium Lactate 0
10 0 0 0 15 0 Sorbitol 0 0 0 0 10 0 0 Glycerol 0 0 0 33 0 0 0
Propylene Glycol 0 0 30 0 0 0 25 Potassium Carbonate 40 40 30 33 40
30 35 Water 40 40 40 34 40 40 40 Properties Freezing Point,
.degree. C. -16 -16 -16 -16 -14 -15 -18
EXAMPLES 54-61
[0077] Additional deicing and anti-icing fluids containing
potassium carbonate were prepared in accordance with the present
invention and measured for BOD and COD values. The results are set
forth below in Table 4. For comparative purposes, the COD and BOD
for a 50/50 glycol/water mixture also are provided. Also, for
reference the COD and BOD, respectively, for the individual
components are as follows: methyl glucoside (1.24, 0.71), sodium
lacate (0.86, 0.51), potassium lactate (0.75, 0.45), sorbitol
(1.14, 0.70), propylene glycol (1.68, 1.14) potassium carbonate
(0.00, 0.00), water (0.00, 0.00).
6TABLE 4 Example 54 55 56 57 58 59 60 61 Composition Methyl 10 10 0
0 0 15 0 0 Glucoside Sodium 10 0 0 0 10 0 0 0 Lactate Potassium 0
10 0 0 0 15 0 0 Lactate Sorbitol 0 0 0 0 10 0 0 0 Glycerol 0 0 0 33
0 0 0 0 Propylene 0 0 30 0 0 0 25 50 Glycol Potassium 40 40 30 33
40 30 35 0 Carbonate Water 40 40 40 34 40 40 40 50 Properties COD
kg/kg 0.21 0.20 0.50 0.40 0.20 0.30 0.42 0.84 BOD kg/kg 0.12 0.12
0.34 0.24 0.12 0.17 0.29 0.57
EXAMPLE 62
[0078] A useful formulation for non-chloride liquid deicing
consists of a solution in water of approximately 34-weight percent
potassium acetate, 7.9 weight percent propylene glycol, 0.5 weight
percent corrosion inhibitor and the balance water. This formulation
has a freezing point of -40.degree. F. The following table shows
two cases. In case 62A, the formula is prepared from potassium
acetate purchased at the normal commercial strength of 50 weight
percent. In case 62B, potassium acetate is produced at or near the
airport site by dissolving dry KOH in storm water and adding the
requisite quantity of glacial acetic acid. The glycol in both cases
is provided from two sources--(1) a recovered airport storm water
containing 10 weight percent glycol, and (2) purchased commercial
90 weight percent glycol. Table 5 below shows the proportions of
raw material required for each case.
7 62A 62B 50% potassium acetate 64.0 0.0 solid potassium hydroxide
0.0 18.3 glacial acetic acid 0.0 19.6 purchased 90% propylene
glycol 5.5 2.2 recovered storm water - 30.0 59.4 10% propylene
glycol inhibitor 0.5 0.5 Total 100.0 100.0
[0079] The advantages of operating in the manner of Example 62B
are:
[0080] A principal objective of this operation is to dispose of as
much dilute storm water as possible. Case 62B consumes almost twice
as much storm water per unit of deicing fluid produced and
sold.
[0081] Further to this same point, the storm water often has a
negative value since the airport often must pay to have the
municipal water treatment facilities handle this material.
[0082] The reduced quantity of purchased commercial glycol results
in a lower cost product.
[0083] Eliminating double shipment and the shipment of water in the
50% commercial product reduces the potassium acetate cost.
[0084] From the above data it can be seen that excellent deicing
and/or anti-icing materials can be obtained in accordance with the
present invention.
[0085] Many variations of the present invention will suggest
themselves to those skilled in the art in light of the
above-detailed description. For example, any industrial or
agricultural process stream that contains carboxylic acid salts,
hydroxycarboxylic acid salts and/or dicarboxylic acid salts may be
used to prepare the compositions of the present invention.
Additionally, a wide variety of glucosides, carbonates, hydrocarbyl
aldosides, and a variety of combinations of the components of the
present invention may be employed in the compositions of the
present invention. All such obvious modifications are within the
full-intended scope of the appended claims.
[0086] The above-referenced patents, patent applications, test
methods and publications are hereby incorporated by reference.
* * * * *