U.S. patent application number 14/849991 was filed with the patent office on 2015-12-31 for hydroxycarboxylic acids and salts.
The applicant listed for this patent is THE UNIVERSITY OF MONTANA. Invention is credited to Kirk R. Hash, Donald E. Kiely, Kylie Kramer-Presta, Tyler N. Smith.
Application Number | 20150376104 14/849991 |
Document ID | / |
Family ID | 41132406 |
Filed Date | 2015-12-31 |
United States Patent
Application |
20150376104 |
Kind Code |
A1 |
Kiely; Donald E. ; et
al. |
December 31, 2015 |
HYDROXYCARBOXYLIC ACIDS AND SALTS
Abstract
Compositions which inhibit corrosion and alter the physical
properties of concrete (admixtures) are prepared from salt mixtures
of hydroxycarboxylic acids, carboxylic acids, and nitric acid. The
salt mixtures are prepared by neutralizing acid product mixtures
from the oxidation of polyols using nitric acid and oxygen as the
oxidizing agents. Nitric acid is removed from the hydroxycarboxylic
acids by evaporation and diffusion dialysis.
Inventors: |
Kiely; Donald E.; (Missoula,
MT) ; Hash; Kirk R.; (Drummond, MT) ;
Kramer-Presta; Kylie; (Missoula, MT) ; Smith; Tyler
N.; (Missoula, MT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE UNIVERSITY OF MONTANA |
MISSOULA |
MT |
US |
|
|
Family ID: |
41132406 |
Appl. No.: |
14/849991 |
Filed: |
September 10, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12422135 |
Apr 10, 2009 |
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14849991 |
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11890760 |
Aug 6, 2007 |
7692041 |
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12422135 |
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60836329 |
Aug 7, 2006 |
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Current U.S.
Class: |
252/70 ;
562/582 |
Current CPC
Class: |
C09K 3/185 20130101;
C07H 3/04 20130101; C04B 24/06 20130101; C23F 11/126 20130101; C07C
59/105 20130101; C07H 3/02 20130101; C07H 3/06 20130101; C08B 37/00
20130101; C04B 2103/61 20130101; C07C 51/412 20130101; C07C 51/316
20130101 |
International
Class: |
C07C 51/31 20060101
C07C051/31; C09K 3/18 20060101 C09K003/18; C04B 24/06 20060101
C04B024/06; C07C 59/105 20060101 C07C059/105; C07C 51/41 20060101
C07C051/41 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] The invention was made with Government support under Grant
No. 2003-364463-13003 and 2005-364463-15561 awarded by the
USDA-CSRESS. The Government has certain rights in the invention.
Claims
1. A corrosion inhibiting composition for metal comprising at least
one organic acid salt prepared by a method comprising the steps of:
a) preparing an aqueous solution of at least one organic compound
suitable for nitric acid oxidation; b) combining, over time, the
aqueous solution of the at least one organic compound and an
aqueous solution of nitric acid to oxidize the at least one organic
compound to at least one organic acid; c) removing a portion of the
nitric acid from the combined aqueous solution through an
evaporation process; and d) making basic with at least one base the
solution from which nitric acid has been removed to convert
residual nitric acid to inorganic nitrate and to convert the at
least one organic acid to the at least one organic acid salt.
2. The corrosion inhibiting composition of claim 1, wherein said
the at least one organic compound suitable for nitric acid
oxidation is selected from the group consisting of diols, triols,
polyols, and carbohydrates.
3. The corrosion inhibiting composition of claim 1, wherein said
method further comprises the steps of, after step c): removing
additional nitric acid from the combined aqueous solution by
diffusion dialysis.
4. The corrosion inhibiting composition of claim 1, wherein said at
least one organic acid comprises glucaric acid, said method further
comprises the steps of, after step c): adding a potassium base to
the solution from which nitric acid has been removed to neutralize
residual nitric acid and to convert a portion of the glucaric acid
to glucaric acid monopotassium salt; and removing at least some of
the glucaric acid monopotassium salt from said at least one organic
acid.
5. The corrosion inhibiting composition of claim 4, wherein said
potassium base is selected from the group consisting of: potassium
hydroxide, potassium hydride, potassium carbonate, potassium
bicarbonate, dipotassium phosphate, tripotassium phosphate, and
potassium acetate.
6. The corrosion inhibiting composition of claim 3, wherein said at
least one organic acid comprises glucaric acid, said method further
comprises the steps of, after diffusion dialysis: adding a
potassium base to the solution from which nitric acid has been
removed to neutralize residual nitric acid and to convert a portion
of the glucaric acid to glucaric acid monopotassium salt; and
removing at least some of the glucaric acid monopotassium salt from
said at least one organic acid.
7. The corrosion inhibiting composition of claim 6, wherein said
potassium base is selected from the group consisting of: potassium
hydroxide, potassium hydride, potassium carbonate, potassium
bicarbonate, dipotassium phosphate, tripotassium phosphate, and
potassium acetate.
8. The corrosion inhibiting composition of claim 1, wherein said at
least one organic acid salt is a neutralized acid selected from the
group consisting of: aliphatic carboxylic acids, hydroxycarboxylic
acids, aldonic acids, uronic acids, aldaric acids, keto-aldonic
acids, keto-uronic acids, keto-aldaric acids, glucaric acid,
mannaric acid, xylaric acid, arabinaric acid, and galactaric
acid.
9. The corrosion inhibiting composition of claim 1, wherein said at
least one organic acid salt is selected from the group consisting
of: sodium potassium D-glucarate dihydrate and dipotassium
D-glucarate hydrate.
10. The corrosion inhibiting composition of claim 1, wherein said
base is selected from the group consisting of: sodium hydroxide,
potassium hydroxide, magnesium hydroxide, calcium hydroxide,
lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium
carbonate, lithium carbonate, calcium carbonate, and magnesium
carbonate.
11. A deicer composition comprising at least one deicing agent and
at least one organic acid salt prepared by a method comprising the
steps of: a) preparing an aqueous solution of at least one organic
compound suitable for nitric acid oxidation; b) combining, over
time, the aqueous solution of the at least one organic compound and
an aqueous solution of nitric acid to oxidize the at least one
organic compound to at least one organic acid; c) removing a
portion of the nitric acid from the combined aqueous solution
through an evaporation process; and d) making basic with at least
one base the solution from which nitric acid has been removed to
convert residual nitric acid to inorganic nitrate and to convert
the at least one organic acid to the at least one organic acid
salt.
12. The deicer composition of claim 11, wherein said the at least
one organic compound suitable for nitric acid oxidation is selected
from the group consisting of diols, triols, polyols, and
carbohydrates.
13. The deicer composition of claim 11, wherein said method of
further comprises the steps of after step c): removing additional
nitric acid from the combined aqueous solution by diffusion
dialysis.
14. The deicer composition of claim 11, wherein said at least one
organic acid comprises glucaric acid, said method further comprises
the steps of, after step c): adding a potassium base to the
solution from which nitric acid has been removed to neutralize
residual nitric acid and to convert a portion of the glucaric acid
to glucaric acid monopotassium salt; and removing at least some of
the glucaric acid monopotassium salt from said at least one organic
acid.
15. The deicer composition of claim 14, wherein said potassium base
is selected from the group consisting of: potassium hydroxide,
potassium hydride, potassium carbonate, potassium bicarbonate,
dipotassium phosphate, tripotassium phosphate, and potassium
acetate.
16. The deicer composition of claim 13, wherein said at least one
organic acid comprises glucaric acid, said method further comprises
the steps of, after diffusion dialysis: adding a potassium base to
the solution from which nitric acid has been removed to neutralize
residual nitric acid and to convert a portion of the glucaric acid
to glucaric acid monopotassium salt; and removing at least some of
the glucaric acid monopotassium salt from said at least one organic
acid.
17. The deicer composition of claim 16, wherein said potassium base
is selected from the group consisting of: potassium hydroxide,
potassium hydride, potassium carbonate, potassium bicarbonate,
dipotassium phosphate, tripotassium phosphate, and potassium
acetate.
18. The deicer composition of claim 11, wherein said at least one
organic acid salt is a neutralized acid selected from the group
consisting of: aliphatic carboxylic acids, hydroxycarboxylic acids,
aldonic acids, uronic acids, aldaric acids, keto-aldonic acids,
keto-uronic acids, keto-aldaric acids, glucaric acid, mannaric
acid, xylaric acid, arabinaric acid, and galactaric acid.
19. The deicer composition of claim 11, wherein said at least one
organic acid salt is selected from the group consisting of: sodium
potassium D-glucarate dihydrate and dipotassium D-glucarate
hydrate.
20. The deicer composition of claim 11, wherein said at least one
base is selected from the group consisting of: sodium hydroxide,
potassium hydroxide, magnesium hydroxide, calcium hydroxide,
lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium
carbonate, lithium carbonate, calcium carbonate, and magnesium
carbonate.
21. The deicer composition of claim 11, wherein said at least one
deicing agent is selected from the group consisting of: sodium
chloride, magnesium chloride, sodium acetate, potassium acetate,
calcium magnesium acetate, and calcium chloride.
22. A concrete admixture composition comprising at least one
organic acid salt prepared by a method comprising the steps of: a)
preparing an aqueous solution of at least one organic compound
suitable for nitric acid oxidation; b) combining, over time, the
aqueous solution of the at least one organic compound and an
aqueous solution of nitric acid to oxidize the at least one organic
compound to at least one organic acid; c) removing a portion of the
nitric acid from the combined aqueous solution through an
evaporation process; and d) making basic with at least one base the
solution from which nitric acid has been removed to convert
residual nitric acid to inorganic nitrate and to convert the at
least one organic acid to the at least one organic acid salt.
23. The concrete admixture composition of claim 22, wherein said
the at least one organic compound suitable for nitric acid
oxidation is selected from the group consisting of diols, triols,
polyols, and carbohydrates.
24. The concrete admixture composition of claim 22, wherein said
method further comprises the steps of, after step c): removing
additional nitric acid from the combined aqueous solution by
diffusion dialysis.
25. The concrete admixture composition of claim 22, wherein said at
least one organic acid comprises glucaric acid, said method further
comprises the steps of, after step c): adding a potassium base to
the solution from which nitric acid has been removed to neutralize
residual nitric acid and to convert a portion of the glucaric acid
to glucaric acid monopotassium salt; and removing at least some of
the glucaric acid monopotassium salt from said at least one organic
acid.
26. The concrete admixture composition of claim 25, wherein said
potassium base is selected from the group consisting of: potassium
hydroxide, potassium hydride, potassium carbonate, potassium
bicarbonate, dipotassium phosphate, tripotassium phosphate, and
potassium acetate.
27. The concrete admixture of claim 24, wherein said at least one
organic acid comprises glucaric acid, said method further comprises
the steps of, after diffusion dialysis: adding a potassium base to
the solution from which nitric acid has been removed to neutralize
residual nitric acid and to convert a portion of the glucaric acid
to glucaric acid monopotassium salt; and removing at least some of
the glucaric acid monopotassium salt from said at least one organic
acid.
28. The concrete admixture composition of claim 27, wherein said
potassium base is selected from the group consisting of: potassium
hydroxide, potassium hydride, potassium carbonate, potassium
bicarbonate, dipotassium phosphate, tripotassium phosphate, and
potassium acetate.
29. The concrete admixture composition of claim 22, wherein said at
least one organic acid salt is a neutralized acid selected from the
group consisting of: aliphatic carboxylic acids, hydroxycarboxylic
acids, aldonic acids, uronic acids, aldaric acids, keto-aldonic
acids, keto-uronic acids, keto-aldaric acids, glucaric acid,
mannaric acid, xylaric acid, arabinaric acid, and galactaric
acid.
30. The concrete admixture composition of claim 22 wherein said at
least one organic acid salt is selected from the group consisting
of: sodium potassium D-glucarate dihydrate and dipotassium
D-glucarate hydrate.
31. The concrete admixture composition of claim 22, wherein said
base is selected from the group consisting of: sodium hydroxide,
potassium hydroxide, magnesium hydroxide, calcium hydroxide,
lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium
carbonate, lithium carbonate, calcium carbonate, and magnesium
carbonate.
32. The concrete admixture composition of claim 22, wherein said
admixture serves as a concrete set retarder.
33. The concrete admixture composition of claim 22, wherein said
admixture serves as a concrete water reducer.
34. The concrete admixture composition of claim 22, wherein said
admixture serves as a concrete set retarder and water reducer.
35. A method for preparing an aqueous solution of at least one
organic compound suitable for direct nitric acid oxidation
comprising the steps of: adding at least one polysaccharide to
aqueous nitric acid; stirring the resulting mixture until the
polysaccharide is hydrolyzed to lower molecular weight saccharides
selected from the group consisting of: smaller than the at least
one polysaccharide, oligosaccharides, tetrasaccharides,
trisaccharides, disaccharides, and monosaccharides.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application of
co-pending application Ser. No. 11/890,760, filed Aug. 6, 2007,
which claims the benefits of U.S. Provisional Patent Application
No. 60/836,329, filed Aug. 7, 2006, the disclosure of which is
hereby incorporated by reference in its entirety including all
figures, tables and drawings.
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM
LISTING COMPACT DISC APPENDIX
[0003] Not applicable
BACKGROUND OF THE INVENTION
[0004] This invention describes a method for synthesizing
hydroxycarboxylic acid salts from polyols using nitric acid and
oxygen as the oxidizing agents and applying the hydroxycarboxylic
acid salts for uses that include corrosion inhibiting materials and
components of concrete.
[0005] Hydroxycarboxylic acids and hydroxycarboxylic acid salts are
well recognized as corrosion inhibitors particularly effective in
inhibiting metal corrosion when the metal is in contact with water
or an aqueous solution (U.S. Pat. No. 2,529,177; U.S. Pat. No.
2,529,178; Erasmus, 1971; Marukume, 1993; Hashimoto, 1976; and U.S.
Pat. No. 4,120,655).
[0006] Nieland et al. taught that these hydroxycarboxylic acids, or
salts thereof, may contain a single carboxylic acid function, as in
the case of gluconic acid (U.S. Pat. No. 2,529,178), or multiple
carboxylic acid functions as in the case of tartaric acid, a
hydroxydicarboxylic acid, or citric acid, a hydroxytricarboxylic
acid (U.S. Pat. No. 2,529,170). Nieland et al. have also taught
that hydroxycarboxylic acids, or salts thereof, with multiple
carboxylic acid functions, such as tartaric acid (U.S. Pat.
2,529,170), generally exhibit better corrosion inhibition
properties than do comparable hydroxymonocarboxylic acids, such as
gluconic acid (U.S. Pat. No. 2, 529,178).
[0007] Hydroxycarboxylic acids have also been shown to inhibit
metal corrosion in aqueous salt brine such as sea water (Mor, 1971;
Mor 1976; and Wrubl, 1984) or formulated brine solutions
(Kuczynski, 1979; Korzh, 1981; Sukhotin, 1982; and Abdallah, 1999),
some employed for specific applications, such as in industrial
cooling systems (Sukhotin, 1982).
[0008] Metal corrosion inhibitors are commonly mixtures of
components that include hydroxycarboxylic acids, or salts thereof,
the mixtures sometimes described as providing a synergistic or
cooperative effect with components other than hydroxycarboxylic
acids in corrosion inhibition rendering corrosion inhibition
properties better than and/or different from the individual
components.
[0009] Crambes et al. describe (U.S. Pat. No. 4,120,655) the use of
hydroxycarboxylic acids selected from the group tartaric, citric
and gluconic in addition to a phosphoric acid ester of an
alkanolamine to inhibit the corrosion of ferrous metals in aqueous
media including aqueous media with high salt content. Numerous
additional examples of the use of hydroxycarboxylic acids or
hydroxycarboxylic salts in mixtures with components other than
hydroxycarboxylic acids that serve as corrosion inhibiting agents
have been reported (U.S. Pat. Nos. 3,589,859; 3,711,246; 4,108,790;
5,891,225; 5,531,931; 5,330,683; and Foroulis, 1971; Foroulis,
1972; Foroulis, 1973; Hiroshige, 1973; and Birk, 1976).
[0010] Sufrin et al. (U.S. Pat. No. 5,330,683) claims use of
gluconate, with additional components that include sorbitol or
mannitol, as a corrosion inhibition agent in brine. However, it is
clear from earlier reports (Mor, 1971; Mor 1976; Wrubl, 1984; and
Kuczynsiki, 1979) that gluconate had been reported effective as a
corrosion inhibitor in brine.
[0011] Hydroxycarboxylic acids or salts thereof have a documented,
long history of use as corrosion inhibitors in liquid and solid
media. They can function as corrosion inhibitors for metals in
contact with water or aqueous solutions. They can serve as
corrosion inhibitors in aqueous solutions that have low to high
salt concentrations, wherein those salts include, but are not
limited to alkali or alkaline metal salts of halides or other
anionic components. They can function as corrosion inhibitors in
the absence or presence of added substances. When they function as
corrosion inhibitors in the presence of added substances the added
substances may provide a positive synergistic corrosion inhibitory
effect. Hydroxycarboxylic acids or salts forms with a single
carboxylic acid function or multiple carboxylic acid functions can
perform as corrosion inhibitors. Salt forms of these
hydroxycarboxylic acids as corrosion inhibitors may have different
cation components such as, but not limited to, alkali and alkaline
earth cations. Hydroxycarboxylic acids or salt forms can serve as
corrosion inhibitors against a number of metals, including, but not
limited to iron, aluminum, copper and zinc. The hydroxycarboxylic
acids or salt forms can serve as corrosion inhibitors in a
multitude of applications where the use of nontoxic agents is an
important advantage or requirement in the application, including
but not limited to: cleaning of metal equipment; as corrosion
inhibiting agents with corrosive salts, or other materials; for
deicing purposes on surfaces in cold weather; in applications
involving storage or transport of water or aqueous solutions in
metal containers or conduits; in concrete and concrete containing
metal components such as structural steel bars.
[0012] A need however remains for the availability of
environmentally desirable materials for use as corrosion inhibiting
agents for a variety of applications. Furthermore, it is clear that
there is a need for such materials on a commercial scale for
applications that include, but are not limited to, corrosion
inhibiting agent in use with deicing agents for use on roadways and
pedestrian walkways affected by snow and ice during cold weather
periods, for use in concrete in contact with metal reinforcing
bars, for cleaning boilers and other metal equipment. Materials
that employ good corrosion inhibiting characteristics, are
environmentally desirable, and can be produced economically on a
large scale would be welcomed for commercial application on a large
scale.
[0013] Hydroxycarboxylic acids and hydroxycarboxylic salts are also
widely described as admixtures to concrete used to favorably
influence different characteristics of concrete. Hydroxycarboxylic
acids as admixtures (additives) to concrete formulations can serve
to favorably effect how the concrete is applied and provide
favorable characteristics of the concrete once it has hardened and
is in use. Concrete admixtures include but are limited to roles as
high-performance water reducers, improve concrete strength, and
improve slump contraction (Wang, 2007). Such materials have been
employed as set retarding additives (U.S. Published Patent
Application No. US 2005-271431), as a set retarder for downhole use
(Drochon, 2003), as components to aid in production of rapid
setting cement (U.S. Published Patent Application No. 2002-228008),
as components of aqueous cementing fluids to increase compression
strength (U.S. Published Patent Application No. 2;004-822459), as a
setting controlling agent (e.g. tartaric acid, K Na tartrate, and
trisodium citrate) for use in production of cement hardened body
(Sakamoto, 2004), as a component of a blowing material for
repairing degraded concrete (Araki, 2003), as a component of a
plasticizer or superplasticizer in cement (Cerulli, 2002), as a
component of a water-proof agent for concrete (Wu, 1999), as
components of low-shrinkage cements useful for paving (Sekiguchi,
1993), as components of lightweight cellular cement articles
(Sakurada, 1989), as a component of a rust-preventing composition
in cement for steel reinforcement (Nakano, 1986), as components of
refractory cements for use at high temperatures (Denki, 1985), as a
component of rapidly hardening cement (Denki II, 1985), as a
component for retarding the setting of cement mortars for large
deep wells (Ene, 1982). The polyhydroxycarboxylic acids used as
components of the setting retardants described in Ene were prepared
by oxidation of molasses with nitric acid at 90.degree. C. followed
by neutralization.
[0014] Consequently, it is clear that there is a need for
polyhydroxycarboxylic acids and their salts on a commercial scale
for concrete production applications as illustrated herein and
include but are not limited to those uses, as they reflect only a
portion of the reported uses in conjunction with concrete. Such
materials are also environmentally desirable in concrete and in
related mortar applications, and their large scale economic
production would be welcomed for commercial application on a large
scale.
[0015] Salts of glucaric acid are also sold as food supplements.
Monopotassium glucarate (potassium hydrogen glucarate) is used to
maintain healthy cholesterol levels already within normal ranges,
whereas calcium D-glucarate is used to promote glucuronidation, a
process in which the body eliminates toxins and other adverse
substances (U.S. Pat. Nos. 4,845,123; 5,561,160; and 5,364,644).
Monopotassium glucarate has a relatively low water solubility
(about 10%) and calcium D-glucarate is very insoluble in water.
Therefore water soluble dipotassium D-glucarate hydrate (Styron,
2002) and monosodium monopotassium D-glucarate dihydrate (Styron,
2002) offer opportunities as food supplements and other
applications where their water solubility is advantageous, and
preferred over the less water soluble glucarate salts.
[0016] Given the long documented history of the effectiveness of
hydroxycarboxylic acids as corrosion inhibitors and as components
of cement and products therefrom, and their attraction as materials
for safe use in the environment, it is desirable to have these
materials available in large quantities for numerous applications.
It is also desirable to be able to employ a single, basic
technology to the oxidation of these varied polyols for the
production of the desired hydroxycarboxylic acid salt products for
use as corrosion inhibiting materials or concrete admixture
materials. Furthermore, it is desirable to be able to apply the
technology to a variety of polyol or carbohydrate feedstocks to
produce oxidation products with attractive properties that extend
beyond those cited here. The currently employed commercial methods
of preparation of the common hydroxycarboxylic acids or salts
thereof are principally biologically induced transformations or
fermentations, as for example in the production of tartaric acid
(U.S. Pat. No. 2,314,831), gluconic acid (U.S. Pat. No. 5,017,485),
and citric acid (U.S. Pat. No. 3,652,396). The fermentation of
suitable carbohydrate feedstocks for fermentation to the target
acid requires specific microorganisms and special conditions to
effect each of the fermentations, which are complex and multistep
processes (Wisconsin Biorefiners).
[0017] All patents, patent applications, provisional patent
applications and publications referred to or cited herein, are
incorporated by reference in their entirety to the extent they are
not inconsistent with the teachings of the specification.
BRIEF SUMMARY OF THE INVENTION
[0018] This invention describes novel chemical oxidation methods
for polyols to prepare hydroxycarboxylic acids, as single oxidation
products or in mixtures of oxidation products, applicable to
commercial scale production. The invention also describes
conversion of the oxidation products to mixtures of salt products
or to individual salt products. The oxidation products can be used
as corrosion inhibiting materials for a variety of corrosion
inhibiting applications, as concrete admixtures, and for other
applications that can take advantage of the properties of the
product mixtures or pure organic compounds isolated from the
mixtures. The preferred chemical oxidation method employs nitric
acid as the oxidizing agent in aqueous solution. The oxidation
method is applicable to polyols in general, of which carbohydrates
provide multiple and diverse structurally different examples.
DETAILED DESCRIPTION OF THE INVENTION
[0019] This invention is directed to the chemical preparation of
hydroxycarboxylic acids, as single oxidation products or as
mixtures of oxidation products, applicable to commercial scale
production, and employing the oxidation products as corrosion
inhibiting materials for a variety of corrosion inhibiting
applications, as components of concrete, and for any other
applications that can take advantage of the availability of these
oxidation products.
[0020] Hydroxycarboxylic acids can be considered as oxidation
derivatives of carbohydrates or other polyols, a polyol meaning any
organic compound with two or more alcohol hydroxyl groups. Such
carbohydrates or polyols include, but are not limited to: simple
aldoses and ketoses such as glucose, xylose or fructose; simple
polyols such as glycerol, sorbitol or mannitol; reducing
disaccharides such as maltose, lactose, or cellobiose; reducing
oligosaccharides such as maltotriose, maltotetrose, or
maltotetralose; nonreducing carbohydrates such as sucrose,
trehalose and stachyose; mixtures of monosaccharides and
oligosaccharides (that may include disaccharides); glucose syrups
with different dextrose equivalent values; polysaccharides such as,
but not limited to, starch, cellulose, arabinogalactans, xylans,
mannans, fructans, hemicelluloses; mixtures of carbohydrates and
other polyols that include one or more of the carbohydrates or
polyols listed above.
[0021] The preferred chemical oxidation method employs nitric acid
as the oxidizing agent in aqueous solution and has been described
(U.S. Published Patent Application 2008/0033205). The nitric acid
oxidation process described in Kiely and Hash (U.S. Published
Patent Application 2008/0033205) has two main components; an
oxidation process, followed by separation of nitric acid from
organic products mixture, the organic products mixture being
primarily composed of hydroxycarboxylic acids. The final organic
products mixture can be further treated to generate an organic
acids products mixture for use in acid forms or salt forms, or
individual isolated hydroxyacid products for use in acid or salt
forms.
[0022] Applying the nitric acid oxidation method (U.S. Published
Patent Application 2008/0033205) to a glucose containing solution,
produces a mixture of oxidation products that includes gluconic
acid, glucaric acid, tartaric acid, tartronic acid, 5-ketogluconic
acid, and glyceric acids, all of which are hydroxycarboxylic acids.
It was anticipated that such a mixture, water soluble and in salt
form, would have some effectiveness in iron corrosion inhibition
tests. Employing standard iron corrosion inhibition testing as
described here, it was determined that glucarate, from the
hydroxydicarboxylic acid D-glucaric acid, was a more effective
corrosion inhibiting agent than was gluconate, from the
hydroxymonocarboxylic acid D-gluconic acid, as expected from the
report of Neiland et al. (U.S. Pat. Nos. 2,529,177; and 2,529,178)
that hydroxydicarboxylic acids display greater corrosion inhibiting
characteristics than hydroxymonocarboxylic acids. When the complex
oxidation product mixture in salt form was evaluated for corrosion
inhibition performance, it was found surprisingly that the mixture
was close in corrosion inhibition effectiveness to that of
glucarate alone, and more effective than gluconate alone (Table 1).
However, what was more surprising was that when a portion of the
high valued glucarate had been removed from the oxidation mixture
the effectiveness of the remaining product as a corrosion inhibitor
was comparable to product mixture before the glucarate had been
removed (Table 2). Since the dicarboxylic acid salt, such as a
D-glucarate salt, is a more effective corrosion inhibitor than its
corresponding monohydroxycarboxylic acid salt, a D-gluconate salt,
it was fully expected that the material from which D-glucarate had
been removed would be a less effective corrosion inhibitor than the
material that still contained all of the glucarate. This finding
adds economic value to the process since the high value D-glucaric
salts can be removed from the oxidation leaving behind mixtures
with corrosion inhibiting properties that are comparable to the
mixtures with D-glucarate retained. The corrosion inhibiting
effectiveness testing results (Table 1) also demonstrate that
oxidation mixtures from structurally variable polyols also show
good properties as corrosion inhibition agents. Thus, it has been
determined that the chemical oxidation process gives rise to a
complex product mixture, and that mixture can be used effectively
as a corrosion inhibitor, with all of the higher valued D-glucarate
in the mixture, or with some of the D-glucarate removed.
Furthermore, it is clear that the nitric acid oxidation of the
polyols using nitric acid as the oxidizing agent and reaction
solvent, can successfully generate mixtures of oxidized organic
acids, which in salt form, can be used directly as effective
corrosion inhibiting agents without any need for purification
beyond removal of the nitric acid as described (U.S. Published
Patent Application 2008/0033205). The oxidative conversion of
polyols to mixtures of hydroxycarboxylic acids with nitric acid
offers for the first time a method for a rapid and effective large
scale production method of these acids in salt form as cost
effective and environmentally desirable corrosion inhibition agents
and as beneficial cement components.
[0023] In addition to the oxidation product mixtures here described
for use in corrosion inhibition applications, components of
concrete and for other purposes, it is also desirable to use the
oxidation process to prepare solid pure materials for particular or
special applications that include, but are not limited to,
corrosion inhibition in deicing applications such as when applied
to surfaces for pedestrian or automotive use. It is desirable that
such materials have, in addition to their corrosion inhibiting
characteristics and environmentally favorable properties,
crystalline properties, as opposed to being solid powders.
Furthermore, it is advantageous that such materials be readily
water soluble in order to perform well as corrosion inhibition
materials in the presence of water and water and ice/snow.
Crystalline materials mix well with solid deicers such as, but not
limited to, sodium chloride or magnesium chloride, and allow for
normal spreading of the solid deicer and crystalline corrosion
inhibitor without concern for the corrosion inhibiting agent being
blown about and not applied properly. Two such highly crystalline
forms of glucarate which can be produced from the nitric acid
oxidation method of glucose containing starting materials are
dipotassium D-glucarate hydrate and monosodium monopotassium
D-glucarate dihydrate, respectively (Styron, 2002). These materials
have crystalline properties that make them very suitable for
corrosion inhibition methods that employ solids, and in particular
in combination with solid deicers. These materials are also readily
soluble in water, making them very useful as corrosion inhibiting
agents in aqueous solution.
[0024] Salts of glucaric acid are also sold as food supplements.
The two widely sold salts of D-glucaric acid are monopotassium
D-glucarate (potassium hydrogen D-glucarate) and calcium
D-glucarate (U.S. Pat. Nos. 4,845,123; 5,561,160; and 5,364,644),
respectively, the former to maintain healthy cholesterol levels
already within normal ranges, and the latter to promote
glucuronidation, a process in which the body eliminates toxins and
other adverse substances. Monopotassium D-glucarate has a
relatively low water solubility (about 10%), is a powdery
substance, and solid calcium D-glucarate is very insoluble in
water. Therefore nicely crystalline and water soluble dipotassium
D-glucarate hydrate and monosodium monopotassium D-glucarate
dihydrate (Styron, 2002), available from the oxidation process
described here and potentially in large amounts as co-products of
the even larger commercial oxidation mixtures products markets
employing the mixtures in non-food applications, such as corrosion
inhibiting agents and components of cement. Overall, these latter
salts offer opportunities and advantages in whatever applications
can use them as cost effective, water soluble hydroxyacids, and in
some specific uses, e.g. food supplements, as water soluble
D-glucaric acid salts.
[0025] Producing the mixtures of oxidized polyols employing the
chemical oxidation process as described here has general
advantages. These advantages include that the process is a simple
process, with high recovery of products, that does not require a
purification step to yield the product mixture useful for corrosion
inhibition, concrete production, and other applications that can
take advantage of the properties of the mixtures, beyond the easy
removal of the nitric acid. Additionally, the same basic process
can be employed for all of the desired oxidations employing
suitable carbohydrates or other polyols. The same basic process is
applicable to carbohydrates and other polyols in general, and can
be generally used for oxidations of these feedstocks. The oxidation
product mixture, in its salt form, can be used directly for
corrosion inhibiting applications without costly need for further
purification. The oxidation product mixture, in its salt form
and/or acid form, can be used directly as a component of concrete
without costly need for further purification. The oxidation product
mixture, after removal of a higher valued pure product (or
products), can be used for corrosion inhibiting applications. The
oxidation product mixture, after removal of a higher valued pure
product (or products), can be used for corrosion inhibiting
applications. The oxidation product mixture, after removal of a
higher valued pure product (or products), can be also be used as a
component of concrete. A pure product isolated from the oxidation
mixture can be used for corrosion inhibiting applications or
different applications including as a food supplement. A number of
renewable polyol or carbohydrate feedstocks can be employed as
oxidation substrates to produce hydroxycarboxylic acid products
with corrosion inhibiting characteristics. A number of renewable
polyol or carbohydrate feedstocks can be employed as oxidation
substrates to produce hydroxycarboxylic acid products for use as
components of concrete. The oxidation products formed in these
processes can be used for any number of applications requiring
materials with environmentally desirable properties coupled with
corrosion inhibiting properties. The oxidation products formed in
these processes can be used for any number of applications
requiring materials with environmentally desirable properties
coupled with desirable properties as components of concrete
preparations. The corrosion inhibiting applications include, but
are not limited to: use in water systems with little to no
additional dissolved substances; use in environments in contact
with sea water for corrosion inhibiting applications; use in brine
or water cooling applications; use in boiler and other metal
equipment surface cleaning applications; use as corrosion
inhibiting applications in brine solutions applied for deicing; use
in oil well muds as corrosion inhibiting materials; use in cement
and concrete as corrosion inhibiting materials. The availability of
different mixtures as corrosion inhibiting agents or components of
concrete opens up commercial potential for such mixtures as cost
effective, environmentally favorable materials that can be readily
and efficiently produced from renewable polyols and
carbohydrates.
[0026] The following examples are offered to further illustrate but
not limit both the compositions and the methods of the present
invention. All percentages are by weight and all solvent mixture
proportions are by volume unless otherwise noted.
EXAMPLE 1
Corrosion Test Methods
[0027] Salt products prepared by the nitric acid oxidation methods
and work up procedures described in this invention were evaluated
for their corrosion inhibiting properties according to standard
testing methods. Corrosion tests were performed according to the
National Association of Corrosion Engineers (NACE) Standard
TM0169-95 modified by the Pacific Northwest Snowfighters (PNS)
(NACE TM0169-95).
[0028] The test procedure was modified to use 30 mL of a 3%
solution of inhibitor per square inch of total coupon surface area.
Stamped and numbered steel TSI coupons which met the ASTM F436 Type
1 requirement with a Rockwell hardness of C 38-45 were used for
each corrosion test. Approximate coupon dimensions are 1.37 in.
outer diameter, 0.60 in. inner diameter, and 0.10 in. thickness
with a density of 7.85 grams per cubic centimeter. Coupons were
placed in a sealed container on a rock tumbler with a non-abrasive
cleanser for 30 minutes to remove surface grease and impurities.
Coupons were wiped with acetone to remove any additional grease,
rinsed with deionized water, and then acid etched with an 18.5% HCl
solution for approximately 3 minutes. The coupons were rinsed with
tap water, rinsed with deionized water, patted dry and placed in
chloroform for 15 minutes. The coupons were removed from chloroform
and allowed to air dry in a ventilated hood for 1 hour. Each coupon
was then weighed to the nearest 0.1 mg. at least two times to
ensure a consistent weight.
[0029] Distilled water was used to prepare each solution and
control standard. Sodium chloride was used as the salt standard. A
3% solution of NaCl (EMD, analyzed reagent grade, 9.6 g) in
distilled water (310.4 g) was prepared as a salt standard(w/v).
Each test solution was prepared with 3% NaCl, 310.4 g distilled
water, and a corrosion inhibitor. Two NaCl salt solutions
containing each inhibitor were prepared at 3% and 1.5% inhibitor
concentration (by weight of salt, 288 mg and 144 mg, respectively).
Approximately 300 mL of each solution in distilled water was
transferred to a clean 500 mL Erlenmeyer flask equipped with a
rubber stopper which had been drilled to allow a thin line attached
to a plastic rod to run through it. The pH of each solution was
measured and recorded. Aqueous 5% sodium hydroxide was carefully
added (1-2 drops) until a basic pH was established for each test
solution. The pH of the NaCl and H, O control solutions was not
altered. Three coupons were attached to a plastic bar suspended
within each flask through the stopper hole. A timed device raised
and lowered the test coupons so they were immersed in the test
solution for 10 minutes of each hour for a 72 hour period. Tests
were conducted at room temperature.
[0030] After the 72 h. test period, the coupons were quickly
removed from solution, rinsed under tap water and vigorously rubbed
to remove any surface corrosion material. The coupons were then
placed in shallow evaporating dishes containing a cleaning solution
of concentrated hydrochloric acid, stannous chloride (50 g/liter),
and antimony chloride (20 g/liter) for 15 minutes. The coupons were
removed from the acid solution, rinsed vigorously under tap water,
and returned to the cleaning solution for an additional 15 minutes.
The coupons were again removed from the acid solution, rinsed under
tap water, rinsed under deionized water, patted dry, and placed in
a vessel containing chloroform for 10 minutes. The coupons were
removed from the chloroform and allowed to air dry under a
ventilated hood for 1 hour before being weighed to the nearest 0.1
mg. Each coupon was weighed twice to ensure a true final weight.
Corrosion rate in mils per year (MPY) was calculated from the
measured weight loss of each coupon using the following
equation:
MPY = weight loss ( mg ) 534 area ( cm 2 ) time ( h ) metal density
##EQU00001## metal density = 7.85 g / cc ##EQU00001.2## time = 72
hours ##EQU00001.3##
[0031] The corrosion value for the control solution of distilled
H.sub.2O was also calculated. The MPY value of the distilled water
was subtracted from the MPY value of each sample solution
containing 3% NaCl to provide a corrected MPY value, which is noted
as MPY'. The MPY' values of each of three coupons in the test
solution were averaged to determine the MPY' value of the entire
test solution. A Percent Effectiveness value, which measures the
rate of corrosion of sample as compared to the corrosion value for
salt, was determined. The Percent Effectiveness of each solution is
calculated as follows:
Percent Effectiveness = ( MPY of inhibitor sample - MPY of H 2 O )
( MPY of NaCl - MPY of H 2 O ) 100 ##EQU00002## or ##EQU00002.2##
Percent Effectiveness = MPY 1 of inhibitor sample MPY 1 of NaCl 100
##EQU00002.3##
[0032] Accordingly, the distilled H.sub.2O control has a Percent
Effectiveness value of 0%, while the 3% NaCl control has a 100%
Percent Effectiveness value. The corrosion inhibitor samples have
Percent Effectiveness values between 0% and 100%. In order for a
material to be acceptable as a corrosion inhibitor, the Percent
Effectiveness of the material must have a value of 30% or less as
defined by PNS.
[0033] Table 1 shows corrosion rates (MPY), corrected corrosion
rates (MPY.sup.1), and percent effectiveness of water, 3% NaCI
solution, and 3% NaCl solutions containing corrosion inhibitors
derived from salts of hydroxycarboxylic acids. Each sample was
dissolved in distilled water and the sample solution was made basic
(>pH 8) with the exception of sodium D-gluconate and commercial
liquid sodium gluconate product tested at their natural pH values
of 6.1 and 3.2, respectively.
TABLE-US-00001 TABLE 1 Corrosion Rates (MPY), Corrected Corrosion
Rates (MPY.sup.1), and Percent Effectiveness of Corrosion
Inhibitors in 3% NaCl Solutions* Inhibitor Concentration Percent
Corrosion Inhibitor (%)* MPY MPY.sup.1 Effectiveness None (H.sub.2O
control) 0 5.650 0.000 0.00% sodium D-gluconate 1.5 24.596 20.313
36.98% sodium D-gluconate 3.0 22.786 18.503 33.45% commercial
liquid gluconate product 3.0 34.580 28.928 67.63% sodium potassium
D-glucarate 1.5 23.726 19.443 35.28% sodium potassium D-glucarate
3.0 20.939 16.656 29.84% nitric acid oxidized 95-99% liquid 1.5
24.871 20.588 37.52% dextrose nitric acid oxidized 95-99% liquid
3.0 21.424 15.774 30.78% dextrose nitric acid oxidized 41-44%
liquid 1.5 34.666 29.016 56.63% dextrose nitric acid oxidized
41-44% liquid 3.0 29.904 24.254 47.34% dextrose nitric acid
oxidized sucrose 3.0 21.642 15.992 31.21% None (NaCl control) 0
57.574 51.235 100.00% *Concentrations are given in weight %.
Table 2 shows corrosion rates (MPY), corrected corrosion rates
(MPY.sup.1), and percent effectiveness of water, 3% NaCl solution,
and 3% NaCl solutions containing corrosion inhibitors derived from
nitric acid oxidized 95-99% liquid dextrose and nitric acid
oxidized 95-99% liquid dextrose from which some D-glucarate has
been removed. Each sample was dissolved in distilled water and the
sample solution was made basic (>pH 8).
TABLE-US-00002 TABLE 2 Corrosion Rates (MPY), Corrected Corrosion
Rates (MPY.sup.1), and Percent Effectiveness of Nitric Acid
Oxidized 95-99% Liquid Dextrose and Nitric Acid Oxidized 95-99%
Liquid Dextrose with Less D-Glucarate as Corrosion Inhibitors in 3%
NaCl Solutions* Inhibitor Concentration Percent Corrosion Inhibitor
(%)* MPY MPY.sup.1 Effectiveness H.sub.2O (control) 0.00 5.027
0.000 0.00% nitric acid oxidized 3.25 19.464 14.434 24.03% 95-99%
liquid dextrose nitric acid oxidized 3.25 15.833 10.807 17.99%
95-99% liquid dextrose less D-glucarate nitric acid oxidized 3.90
17.149 12.122 20.18% 95-99% liquid dextrose nitric acid oxidized
3.90 14.568 9.542 15.88% 95-99% liquid dextrose less D-glucarate
nitric acid oxidized 4.55 16.041 11.013 18.33% 95-99% liquid
dextrose nitric acid oxidized 4.55 15.516 10.489 17.46% 95-99%
liquid dextrose less D- glucarate NaCl (control) 0.00 67.238 62.211
100.0% *Concentrations are given in weight %.
[0034] It is clear from the results provided in Tables 1 that by
increasing the concentration of corrosion inhibitor in 3.0% sodium
chloride solution there is a marked improvement (lowering) of the
percent effectiveness (PNS score). It is also clear that the nitric
acid oxidation product from the oxidized 95-99% liquid dextrose
product performs close to that of a pure form of glucarate and
better than gluconate, with the former two materials at about the
preferred 30% effectiveness value and gluconate at a higher value.
The commercial liquid gluconate product showed a very high (poor
performance) corrosion effectiveness score of greater than 60%. The
glucarate and oxidized dextrose materials were adjusted to a higher
pH than gluconate and commercial liquid gluconate because the
former materials have significantly higher water solubility (ca.
70%) than the gluconate product (ca. 60%) at the higher pH, and can
be transported and used at the higher pH value and the
correspondingly higher concentration than can gluconate.
[0035] It has been demonstrated here, and in earlier reports, that
a dihydroxyacid such as D-glucaric acid is a better corrosion
inhibiting agent than the corresponding monohydroxyacid, e.g.,
D-gluconic acid. Consequently, it was anticipated that when the
nitric acid oxidized 95-99% liquid dextrose product used in the
corrosion rate tests had some of the glucarate removed from this
oxidation mixture, the resulting material would be a less effective
corrosion inhibiting material than the material that still
contained all of the glucarate. Surprisingly, contrary to this
obvious expectation, the nitric acid oxidized 95-99% liquid
dextrose less glucarate samples were comparable as corrosion
inhibiting materials to those from nitric acid oxidized 95-99%
liquid dextrose with no glucarate removed (Table 2). This
unexpected result further raises the value of the overall oxidation
process described here, because some high value D-glucaric acid can
first be removed from the oxidation product mixture, leaving a
product mixture that has good corrosion inhibiting properties.
[0036] Consequently, the oxidized products described in this
invention offer several advantages over single hydroxyacids as
corrosion inhibitors that include, but are not limited to: 1) they
have very high water solubilities which allows for lowered cost of
transport and use; 2) they have significantly enhanced performance
at pH values above 7 which decreases the amount of material that is
used in a corrosion inhibiting application and lowers the cost of
that use; 3) they do not require purification to single materials
to effectively inhibit corrosion, an important production cost
lowering factor in their production, 4) some high value D-glucaric
acid can be easily separated from the oxidation mixture of glucose
based substrates, leaving a product behind that offers corrosion
inhibiting properties that are comparable to the mixture that
contained all of the glucaric acid.
EXAMPLE 2
Samples Prepared as Concrete Admixtures
[0037] The samples prepared as concrete admixtures were of the type
listed in Table 2 Sample I being oxidation mixtures as described
with no glucarate removed, Sample II being oxidation mixtures as
described with some glucarate removed, and Sample III being a
single admixture substance from the oxidation, i.e., monopotassium
D-glucarate. [0038] I nitric acid oxidized 95-99% liquid dextrose
[0039] II nitric acid oxidized 95-99% liquid less D-glucarate
[0040] III monopotassium D-glucarate
[0041] A pH greater than 9 was established for Samples I-II by
addition of sodium hydroxide, whereas the pH of the Sample III
solution was established as greater than 9 by addition of potassium
hydroxide.
A.--Admixture Sample Preparation.
[0042] Numerous samples were prepared from the dextrose oxidation
product to be tested as potential concrete admixtures. Each sample
was varied by control of reaction conditions, work-up procedure and
product analysis by ion chromatography for D-glucarate,
D-gluconate, nitrate and additional organic acids in the final
product. Whole product samples (I), whole product with some
D-glucarate removed (II), and single product glucarate (III) were
prepared and submitted for admixture analysis. All samples were
tested and analyzed by TEC Services: Testing, Engineering and
Consulting Services, Inc., 235 Buford Dr., Lawrenceville, Ga.
30045.
B.--Concrete Admixture Test Methods.
[0043] Salt products prepared by the nitric acid oxidation methods
and work up procedures described in this invention were evaluated
for their concrete admixture properties according to standard
testing methods. Admixture tests were performed according to ASTM
Standard C494/C494 M-05a, 2005 "Standard Specifications for
Chemical Admixtures for Concrete", ASTM International, West
Conshohocken, Pa., 2005.
C.--Analysis of Admixtures.
[0044] Standard concrete mixtures of cement, water, rock, sand, and
air entraining agent were prepared for laboratory testing of
concrete admixtures. Approximately 4 L of each sample were prepared
at 20% concentration of solids after being made basic with sodium
hydroxide and submitted for admixture analysis. The mono potassium
D-glucarate product was prepared at 10% solids after being made
basic with potassium hydroxide. Each sample was added to a standard
concrete mixture and tested for performance and efficiency as a
concrete admixture as defined by the ASTM Standard C494/C494 M-05a.
The following physical requirements were measured for each
admixture: water content, slump, percent air, weight, time of
initial and final set, and compressive strength. A concrete sample
without the addition of an admixture was established as a control
sample. Each admixture sample was added to separate concrete test
mixtures and measured against the control. One control mixture and
one trial mixture containing each of the admixtures was prepared
and tested for fresh and hardened concrete properties. Samples were
classified as admixture types as defined by ASTM C494 standards.
There are eight types of admixtures: Type A (water reducing), Type
B (set retarding), Type C (accelerating), Type D (water
reducing/set retarding), Type E (water reducing/accelerating), Type
F (high range water reducing), Type G (high range water
reducing/set retarding), and Type H (mid-range water reducing).
Admixture samples were added to the concrete test mixtures in
optimal doses to meet the physical requirements of Type A and Type
D admixtures. Samples I-III were also tested as potential Type A
admixtures.
[0045] Type A admixtures maximize the benefits of increased
hydration in hardened and plastic concrete (Collepardi, 1995). The
specifications for Type A water reducing admixtures, as well as the
testing results from Samples I-III are presented in Table 3. As
defined in Section 3 of ASTM C494/C494-05a, Type A admixtures must
reduce the quantity of mixing water required to produce concrete of
given consistency by 5-12% and stay within a defined time of set
comparable to the control, unlike Type D water reducers/set
retarders. Sample I-III were all dosed at approximately 2.5 oz/cwt
cement; however, due the higher concentrations of Samples I and II,
the effective dose (solid admixture amount) was almost twice the
amount of Sample III. While all Samples meet water reduction, time
of set, and compressive strength standards for Type A water
reducters, the higher effective doses of Samples I and II appear to
give better performance as evidenced by the higher percent of water
reduction.
[0046] Type D admixtures encompass the properties of both a set
retarder and a water reducer. To meet specifications, Type D
admixtures must increase the time of set up to 3.5 h and reduce the
amount of requisite mixing water up to 12%. As specified in Table
4, Type D admixtures must meet the compressive strength
requirements of at least 110% of the concrete control. The
specifications for Type D (water reducing/set retarding)
admixtures, as well as the testing results from Samples I-III are
presented in Table 4. Dosage amounts of any admixture are relative
to the amount of cement in the entire concrete mixture. For
example, Sample I was dosed at 2.9 oz/cwt cement in order to meet
the ASTM requirements for a Type D admixture as opposed to the 2.4
oz/cwt required to meet Type A specifications (Table 3). This minor
increase in dosage is significant in defining and applying Sample I
as either a Type D or a Type A admixture. In addition to increasing
the set times, water reduction was also increased at a higher dose
of Sample I. Samples II and III also met Type D admixture standards
at higher doses of 4.0-5.0 oz/cwt cement. Samples I-III meet
compressive strength and durability standards over time. As Type D
admixtures, Samples I-III improve the hardened properties of
concrete and ensure even set. Type D admixtures are essential in
warmer climates, ensuring lengthened time of set and improved
workability while conserving water. Table 4 demonstrates the
effectiveness of Samples I-III as Type D admixtures. Clearly,
changing the dosage of admixtures of Samples I-III, and other
samples of hydroxycarboxylic acids produced using the oxidation
process described here employing a range of process conditions and
from different polyols, underscores the versatility of such
oxidation products as useful for different admixture types.
[0047] In summary, the testing results presented in Tables 3 and 4
illustrate the versatility and effectiveness of products from
oxidation of a polyol with nitric acid as concrete admixtures. As
illustration, Samples I and II are applied at lower concentrations
of solids than most admixtures currently on the market (Collepardi,
1995).
TABLE-US-00003 TABLE 3 Mix Proportions and Test Results for
Dextrose Oxidation Products as Type A (water reducing) Admixtures
Type A Admixture Control I II III Specifications (Concentration)
(0%) (20%) (20%) (10%) (ASTM C494) Cement (lbs/cu yd) 517 517 517
517 512-521 Water (lbs/cu yd) 287.5 270 265 273 .ltoreq.95% of
control Air Entrainment 0.58 0.41 0.39 0.40 (oz/cwt) Admixture Dose
0.0 2.4 2.4 2.5 (oz/cwt) Solid Admixture Amt 0.0 0.48 0.48 0.25
(oz) Glucarate 0.0 40 35 100 Concentration (% of solid) Nitrate
Concentration 0.0 6 4 0.0 (% of solid) Water reduction (% 0.0 6.00
7.58 5.04 .gtoreq.5.0% of control) Slump (in.) 3.50 3.00 3.00 3.00
3''-4'' Air (%) 5.50 5.50 5.00 5.50 5-7 (.+-.0.5 of control)
Initial Set Time 0.00 1:13 later 1:02 later 0:47 later 1:00
earlier-1:30 Difference later Final Set Time 0.00 1:28 later 1:09
later 0:57 later 1:00 earlier-1:30 Difference later Compressive
Strength psi (% of control) 7 days 3150 3650 NA 3930 110% (116%)
(125%)
TABLE-US-00004 TABLE 4 Mix Proportions and Test Results for
Dextrose Oxidation Products as Type D (water reducing/set
retarding) Admixtures Type D Admixture Control I II III
Specifications (Concentration) (0%) (20%) (20%) (10%) (ASTM C494)
Cement (lbs/cu yd) 517 517 517 517 512-521 Water (lbs/cu yd) 287.5
264 273 273 .ltoreq.95% of control Air Entrainment (oz/cwt) 0.58
0.39 0.32 0.34 Admixture Dose (oz/cwt) 0 2.9 5.0 4.8 Solid
Admixture Amt (oz) 0 0.58 1 0.48 Glucarate Concentration 0 40% 28%
100% (% of solid) Nitrate Concentration 0 6% 5% 0% (% of solid)
Water reduction 0.0 8.10 5.04 5.04 .gtoreq.5.0% (% of control)
Slump (in.) 3.5 3.0 3.5 3.5 3''-4'' Initial Set Time 0.00 1:30
later 2:36 later 1:27 later 1:00-3:30 later Difference Final Set
Time Difference 0.00 1:46 later 2:43 later 2:06 later 1:00-3:30
later Compressive Strength, psi (% of control) 7 days 3150 NA 3980
3690 110% (126%) (117%) 28 days 4290 5530 5080 110% (129%)
(118%)
EXAMPLE 3
General Methods
[0048] Solutions were concentrated in vacuo (15-25 mbar) using a
rotary evaporator and water bath at 50.degree. C. pH measurements
were made with a Thermo Orion 310 pH meter (Thermo Fisher
Scientific, Inc., Waltham, Mass., USA) which was calibrated prior
to use. Oxidations were carried out in Mettler Toledo LabMax
reactor, designed to operate as a computer controlled closed-system
reactor. The Labmax was fitted with a top-loading balance, a liquid
feed pump, an oxygen Sierra flow valve, a mechanically driven
stirring rod, a thermometer, a 2 liter thermal jacketed flask, an
FTS recirculating chiller, a pressure manifold fitted with pressure
relief valves and pressure gauge, and a personal computer with
CamileTG v1.2 software. The software installed allows the operator
to program experiments based on specific parameters and conditions.
Oxidation procedures are readily changed as needed as illustrated
in Examples 9-13.
[0049] Examples of, but not limited to, preparation of polyol
aqueous solutions suitable for nitric acid oxidation.
EXAMPLE 4
D-Glucose Solution Preparation
[0050] Aqueous 62.3% D-glucose solution used in the oxidations was
prepared by adding solid D-glucose (325.0 g, 1.50 mol) to 195.0
grams of deionized water in a screw-capped flask containing a stir
bar. Prior to adding solid D-glucose to the water, the water was
heated to ca. 60.degree. C. with stirring. Once the D-glucose was
dissolved, the solution was allowed to cool to ambient temperature
and dry sodium nitrite (1.20 g) was added. The total weight of the
solution was 521.5 g.
EXAMPLE 5
Liquid Dextrose Solution (95-99% Dextrose Equivalent)
Preparation
[0051] Aqueous 62.3% liquid dextrose (95-99% dextrose equivalent)
solution used in the oxidation was prepared by adding semi-solid
liquid dextrose, StaleyDex.RTM. 95 Liquid Dextrose (457.8 g, dry
substance 71.0%) to 62.25 grams of deionized water in a
screw-capped flask containing a stir bar. The flask and its
contents were heated to ca. 60.degree. C. to dissolve the
semi-solid liquid dextrose. Once the liquid dextrose was dissolved,
the solution was allowed to cool to ambient temperature and dry
sodium nitrite (1.20 g) was added. The total weight of the solution
was 521.5 g.
EXAMPLE 6
Lower Dextrose Equivalent (41-45%) Corn Syrup Solution
Preparation
[0052] Aqueous 62.3% liquid corn syrup used in the oxidation was
prepared by adding viscous corn syrup 41-45% dextrose equivalent,
Staley.RTM. 1300 Corn Syrup (404.9 g, dry substance 80.3%) to 115.2
grams of deionized water in a screw-capped flask containing a stir
bar. The flask and its contents were heated to ca. 60.degree. C. to
dissolve the viscous corn syrup. Once dissolved, the solution was
allowed to cool to ambient temperature and dry sodium nitrite (1.20
g) was added. The total weight of the solution was 521.3 g.
EXAMPLE 7
Preparation of a Nitric Acid Hydrolyzed Starch Mixture for Direct
Nitric Acid Oxidation
[0053] Aqueous 50% hydrolyzed starch mixture was prepared by adding
corn starch (50.0 g) in portions (5.0 g) over a 2.25 h period to
35% nitric acid (50.0 g) at 65.degree. C. . The mixture was
suitable for direct nitric acid oxidation as described in Examples
9-13.
EXAMPLE 8
Sucrose Solution Preparation
[0054] The aqueous 62.3% sucrose solution used in the oxidations
was prepared by adding solid sucrose (308.0 g, 0.75 mol) to 184.9
grams of deionized water in a screw-capped flask containing a stir
bar. Prior to adding solid sucrose to the water, the water was
heated to ca. 60.degree. C. with stirring. Once the sucrose was
dissolved, the solution was allowed to cool to ambient temperature
and dry sodium nitrite (1.20 g) was added. The total weight of the
solution was 494.0 g.
[0055] Examples of, but not limited to, nitric acid oxidation of
polyol procedures
EXAMPLE 9
Oxidation Procedure: 1:4 Polyol to Nitric Acid Molar Ratio
[0056] The Recipe Menu was accessed using the Labmax Camille TG
v1.2 software. Stage 1--the temperature was set at 25.degree. C.;
the stirring rod speed set at 200 rpm (and held constant throughout
all remaining stages); time set for 1 minute duration. Stage 2--the
temperature was set at 25.degree. C., and the pressure set at 0.25
bar, time set for 3 minutes. Stage 3--the temperature was set at
25.degree. C., and the pressure set at 0.25 bar above atmosphere,
and 43.3 grams of a 62.3% (w/w) D-glucose solution, containing
0.23% by weight of sodium nitrite, set to be added over 30 minutes.
Stage 4--the temperature was set at 25.degree. C., and the pressure
maintained at 0.25 bar, and the duration was set at 10 minutes.
Stage 5--the temperature was set at 25.degree. C., and the pressure
maintained at 0.25 bar, and 172.9 grams of a 62.3% (w/w) D-glucose
solution, containing 0.23% by weight of sodium nitrite was set to
be added over 90 minutes. Stage 6--the temperature was set at
25.degree. C., and pressure maintained at 0.25 bar, time set for 5
minutes. Stage 7--the temperature was increased to 30.degree. C.,
and the pressure was increased to 0.50 bar, and the time set to 60
minutes duration. Stage 8--the temperature was set at 30.degree.
C., and the pressure maintained at 0.50 bar, and time was set for
over 90 minutes. Stage 9--the reactor temperature was set to cool
to 25.degree. C. over 10 minutes. Once the reaction was programmed
to proceed as indicated, nitric acid (68-70%, 187 mL, ca. 3.0 mol)
was added to the reactor. The reaction recipe was initiated and
starting at stage 1, the reactor was closed to the atmosphere. When
the reaction had progressed through all of the stages, the reaction
mixture was removed from the reactor through the bottom valve of
the reactor.
EXAMPLE 10
Oxidation Procedure: 1:3 Polyol (D-Glucose) to Nitric Acid Molar
Ratio
[0057] The Recipe Menu was accessed using the Labmax Camille TG
v1.2 software. Stage 1--the temperature was set for 25.degree. C.
(and held constant throughout all remaining stages) and the
stirring rod speed set at 200 rpm (and held constant throughout all
remaining stages); 282 mL (68-70%, 4.5 mol) nitric acid was added
to the reactor through a top port; time was set for 1 minute
duration. Stage 2--the pressure was set at 0.25 bar above
atmosphere, time set for 3 minutes duration (and held constant
throughout all remaining stages). Stage 3--added to the nitric acid
was 86.6 grams of a 62.3% (w/w) D-glucose solution containing 0.23%
by weight of sodium nitrite, set to be added over 30 minutes. Stage
4--temperature and pressure held constant for a duration of 10
minutes. Stage 5--added to the nitric acid was 345.8 grams of a
62.3% (w/w) D-glucose solution containing 0.23% by weight of sodium
nitrite, set for a duration of 90 minutes. Stage 6--temperature and
pressure held constant for a duration of 20 minutes. Once the
reaction was programmed to proceed as indicated the reaction recipe
was initiated and starting at stage I, the reactor was closed to
the atmosphere. When the reaction had progressed through all of the
stages, the reaction mixture was removed from the reactor through
the bottom valve of the reactor.
EXAMPLE 11
Oxidation Procedure 1:3 Polyol (95-99% Dextrose Equivalent, Liquid
Dextrose Solution) to Nitric Acid Molar Ratio
[0058] The Recipe Menu was accessed using the Labmax Camille TG
v1.2 software. Stage 1- --the temperature was set for 25.degree. C.
(and held constant throughout all remaining stages) and the
stirring rod speed was set at 200 rpm (and held constant throughout
all remaining stages); 282 mL (68-70%, 4.5 mol) nitric acid was
added to the reactor through a top port; time was set for 1 minute
duration. Stage 2--the pressure was set at 0.25 bar above
atmosphere, time set for 3 minutes duration (and held constant
throughout all remaining stages). Stage 3--added to the nitric acid
was 86.6 grams of a 62.3% (w/w) liquid dextrose solution,
StaleyDex.RTM. 95 solution, containing 0.23% by weight of sodium
nitrite, set to be added over 30 minutes. Stage 4--temperature and
pressure held constant for a duration of 10 minutes. Stage 5--added
to the nitric acid was 345.8 grams of a 62.3% (w/w) liquid dextrose
solution, StaleyDex.RTM. 95, containing 0.23% by weight of sodium
nitrite, set for a duration of 90 minutes. Stage 6--temperature and
pressure held constant for a duration of 20 minutes. Once the
reaction was programmed to proceed as indicated the reaction recipe
was initiated and starting at stage 1, the reactor was closed to
the atmosphere. When the reaction had progressed through all of the
stages, the reaction mixture was removed from the reactor through
the bottom valve of the reactor.
EXAMPLE 12
Oxidation Procedure 1:3 Polyol (41-45% Dextrose Equivalent Corn
Syrup Solution) to Nitric Acid Molar Ratio
[0059] The Recipe Menu was accessed using the Labmax Camille TG
v1.2 software. Stage 1--the temperature was set for 30.degree. C.
(and held constant throughout all remaining stages) and the
stirring rod speed was set at 200 rpm (and held constant throughout
all remaining stages); 282 ml (68-70%, 4.5 mol) nitric acid was
added to the reactor through a top port; time was set for 1 minute
duration. Stage 2--the pressure was set at 0.25 bar above
atmosphere, time set for 3 minutes duration (and held constant
throughout all remaining stages). Stage 3--added to the nitric acid
was 86.6 grams of a 62.3% (w/w) solution of 41-45% dextrose
equivalent corn syrup, Staley.RTM. 1300, solution containing 0.23%
by weight of sodium nitrite, set to be added over 30 minutes. Stage
4--temperature and pressure held constant for a duration of 10
minutes. Stage 5--added to the nitric acid was 345.8 grams of a
62.3% (w/w)) solution of 41-45% dextrose equivalent corn syrup,
Staley.RTM. 1300, solution containing 0.23% by weight of sodium
nitrite, set for a duration of 90 minutes. Stage 6--temperature and
pressure held constant for a duration of 20 minutes. Once the
reaction was programmed to proceed as indicated the reaction recipe
was initiated and starting at stage 1, the reactor was closed to
the atmosphere. When the reaction had progressed through all of the
stages, the reaction mixture was removed from the reactor through
the bottom valve of the reactor.
EXAMPLE 13
Oxidation Procedure 1:6 Polysol of Sucrose to Nitric Acid Molar
Ratio
[0060] The Recipe Menu was accessed using the Labmax Camille TG
v1.2 software. Stage 1--the temperature was set for 35.degree. C.
and the stirring rod speed was 200 rpm (and held constant
throughout all remaining stages); 312.5 ml (68-70%, 5.0 mol) nitric
acid was added to the reactor through a top port; time was set for
1 minute duration. Stage 2--temperature was set at 35.degree. C.,
the pressure was set at 0.25 bar above atmosphere(and held constant
throughout all remaining stages), time set for 3 minutes duration.
Stage 3--temperature was set at 35.degree. C., added to the nitric
acid was 82.2 grams of a 62.3% (w/w) sucrose solution containing
0.23% by weight of sodium nitrite, set to be added over 30 minutes.
Stage 4--temperature was set at 35.degree. C. and time was set for
10 minutes duration. Stage 5--temperature was set at 35.degree. C.,
added to the nitric acid was 328.6 grams of a 62.3% (w/w) sucrose
solution, set for a duration of 90 minutes. Stage 6--temperature
was set at 35.degree. C. and duration was set for 5 minutes. Stage
7--temperature was increased to 40.degree. C. for a duration of 15
minutes. Stage 8--temperature was set at 40.degree. C. and the time
was set for a duration of 20 minutes. Stage 9--the reaction was
allowed to cool to 25.degree. C. for a duration of 10 minutes. Once
the reaction was programmed to proceed as indicated the reaction
recipe was initiated and starting at stage 1, the reactor was
closed to the atmosphere. When the reaction had progressed through
all of the stages, the reaction mixture was removed from the
reactor through the bottom valve of the reactor.
[0061] Examples of, but not limited to, different work up
procedures for removal of nitric acid from a reaction mixture.
EXAMPLE 14
Nitric Acid Removal
[0062] In this work up procedure, the Mech-Chem Diffusion Dialysis
Acid Purification System laboratory scale Model AP-L05 was used to
separate the nitric acid from organic product components in the
reaction mixture (e.g., from Example 9). The Mech-Chem system
contains two metering pumps, the first being the acid reclaim pump
and the second being the acid reject pump. The acid reject pump was
set at 30% (pump length) and 30% (pump speed) and the acid reclaim
pump was set at 40% (pump length) and 40% (pump speed). This put
the reclaim to acid reject ratio at about 1.2. The system was first
primed with RO (reverse osmosis) water according to a standard
setup procedure and then the water was removed from the acid tank
in the unit. The acid tank was then filled with the diluted aqueous
oxidation mixture and the water tank in the unit was filled with RO
water. The acid purification unit was turned on with the pumps set
as indicated and the process initiated. Over time, the diluted
reaction mixture was separated into two distinct streams, the acid
recovery stream and the product recovery stream.
EXAMPLE 15
Nitric Acid Removal
[0063] In this work up procedure, the reaction mixture (e.g., from
Example 10) was concentrated at reduced pressure (rotary
evaporator). The first fraction distilled at ca. 23-34.degree. C.
and 50-120 millibar of pressure and contained NOX gases as
evidenced from the brown color of nitrogen dioxide gas. The NOX
gases were collected using a gas trap cooled with liquid nitrogen.
The concentration of the reaction mixture continued until a viscous
syrup remained. The liquid distillate was weighed (ca. 390 g on
average) and the same amount, ca. 390 g of deionized water was
added to the viscous syrup mother liquor. Further separation of
nitric acid from the organic product was carried out employing
diffusion dialysis. The Mech-Chem Diffusion Dialysis Acid
Purification System laboratory scale model AP-105 was used to
separate nitric acid form the organic product. The same conditions
as described above in Example 14 were employed. Oxidation of liquid
sugar solution as described above was repeated several times, each
reaction mixture was mixed together with an average overall weight
of 2.279 kg. Over a period of 24 hours of processing, the entire
oxidation mixture solution had been collected in either the acid
recovery stream or the product recovery stream.
[0064] Examples of, but not limited to, isolation procedures for
salt products from nitric acid oxidations of polyols illustrated in
examples 9-13 and work up procedures as illustrated in examples
14-15.
EXAMPLE 16
Isolation of Combined Oxidation Products as Sodium Salts from
Nitric Acid Oxidation Example 11, and Work Up Procedure Example
15
[0065] The oxidation procedure described in Example 11 was carried
out three times and the combined oxidation mixtures subjected to
diffusion dialysis as illustrated in Example 15. Total amounts for
the combined oxidation reactions: Staley Dex 95-810.72 g, 4.500 mol
(based upon 100% dextrose); HNO.sub.3--846 mL, 13.5 mol. Upon
completion of the diffusion dialysis, the organic acid solution was
diluted to a total volume of 3.3 L, the reclaimed nitric acid
solution was concentrated to a total volume of 190 mL. These were
labeled as organic acid stock solution and reclaimed nitric acid
stock solution. Organic acid stock solution (300 mL) was chilled in
an ice bath and titrated to a pH of 10 with aqueous NaOH (20 mL,
45% w/w). The solution, which became dark yellow, was allowed to
warm to room temperature. The pH of the solution dropped over time
but was maintained above 9 with additional NaOH (ca. 1 mL). The
resulting solution was refrigerated overnight resulting in a final
pH of 8.3. The solution was concentrated using a rotary evaporator
and dried under reduced pressure for 48 h to give a tan, amorphous
solid. The basification procedure was carried out in triplicate.
The average dried weight of solid product was 66.4 g.+-.1.45 g.
Using this average value, the weight of the crude solid sodium
salts for the total organic acid solution was calculated to be
730.4 g, 90.1% yield by weight.
EXAMPLE 17
Alcohol Precipitation of Combined Oxidation Products as Sodium
Salts from Nitric Acid Oxidation Example 11, and Work Up Procedure
Example 15
[0066] A portion of dried crude solid sodium salt mixture (tan
amorphous solid, ca. 5.0 g) from Example 16 was dissolved in water
(5 mL) to form a viscous amber solution. solution. Methanol (50 mL)
was added to the solution and a tacky solid formed immediately. The
mixture was stirred overnight without change in the appearance of
the composition. The solution was decanted from the solid, and the
solid was washed with methanol (3.times.10 mL) and dried under
reduced pressure. The filtrate and washings were combined,
concentrated using a rotary evaporator, and dried under reduced
pressure. The precipitation procedure was carried out in triplicate
(17a-c, Table 5).
TABLE-US-00005 TABLE 5 Initial Solid Precipitate Dried Filtrate
Recovered Solid Sample Weight (g) Weight (g) Weight (g) Weight (g)
17a 5.0063 4.6326 0.5088 5.1414 17b 5.0047 4.6438 0.5422 5.1860 17c
5.0018 4.6379 0.5500 5.1879
EXAMPLE 18
Isolation of Combined Oxidation Products as Sodium Salts from
Nitric Acid Oxidation Example 12, and Work Up Procedure Example
15
[0067] The oxidation procedure described in Example 12 was carried
out three times and the combined oxidation mixtures subjected to
diffusion dialysis as illustrated in Example 15. Total amounts for
the combined oxidation reactions: Staley 1300-810.72 g, 4.500 mol
(based upon 100% dextrose), HNO.sub.3--846 mL, 13.5 mol. Upon
completion of the diffusion dialysis, the organic acid solution was
diluted to a total volume of 2,640 mL. The streams from diffusion
dialysis were labeled as organic acid stock solution and reclaimed
nitric acid stock solution. Organic acid stock solution (300 mL, pH
1.2) was chilled in an ice bath and titrated to a pH above 10 with
aqueous NaOH (14 mL, 45% w/w). The solution, which became dark
yellow, was allowed to warm to room temperature. The pH of the
solution dropped over time but was maintained above 9 with
additional NaOH (ca. 1 mL). The solution was cooled overnight
resulting in a pH of 8. The solution pH was raised to above 9 with
NaOH, and the solution was concentrated using a rotary evaporator
and then dried under reduced pressure for 48 h to give a golden,
amorphous solid. The basification procedure was carried out in
triplicate. The average dried weight of solid product was 87.8
g.+-.0.62 g. Using this average value, the weight of the crude
solid sodium salts for the total organic acid solution was
calculated to be 772.6 g, 95.3% yield by weight.
EXAMPLE 19
Alcohol Precipitation of Combined Oxidation Products as Sodium
Salts from Nitric Acid Oxidation Example 12, and Work Up Procedure
Example 15
[0068] A portion of dried solid crude sodium salt mixture (ca. 5.0
g) from Example 18, was dissolved in water (5 mL) to form a viscous
amber solution. Methanol (50 mL) was added to the solution and a
fine white precipitate form immediately. The mixture was stirred
overnight during which time most of the syrup had solidified. The
solid was isolated by filtration, washed with methanol (3.times.10
mL), and dried under reduced pressure. The filtrate and washings
were combined, concentrated using a rotary evaporator, and dried
under reduced pressure. The precipitation procedure was carried out
in triplicate (18a-c, Table 6).
TABLE-US-00006 TABLE 6 Initial Solid Precipitate Dried Filtrate
Recovered Solid Sample Weight (g) Weight (g) Weight (g) Weight (g)
18a 5.0094 4.3130 0.8480 5.161 18b 5.0078 4.0448 0.8704 4.9152 18c
5.0073 4.3224 0.8650 5.1874
EXAMPLE 20
Isolation of Monopotassium D-Glucarate (MPG) from Diffusion
Dialysis Organic Acid Solution
[0069] Organic acid stock solution (Example 16, 900 mL, 963.2 g)
was concentrated using a rotary evaporator. The resulting yellow
solution (175 mL, 208.2 g) was diluted to 300 mL. A portion of the
solution (100 mL) was chilled in an ice bath and titrated from a pH
of 1.8 to a pH of 3.7 with aqueous KOH (45% by weight). The
solution was refrigerated overnight during which time a precipitate
formed. The precipitate was isolated by filtration, washed with
cold water (3.times.10 mL), and dried under reduced pressure to
give MPG as a white powder. The precipitation procedure was carried
out in triplicate. The average dried weight of solid product was
6.61 g.+-.0.41 g. Using this average value, the weight of MPG for
the total organic acid solution was calculated to be 72.7 g, 0.293
mol, 9.0% yield by weight.
EXAMPLE 21
Isolation of Combined Oxidation Products, Less MPG in Example 20,
as Potassium/Sodium Salts
[0070] The filtrate and washings from the isolation of
monopotassium D-glucarate (Example 20) were combined and chilled in
an ice bath, then titrated from a pH of 3.8 to a pH of 10 with
aqueous NaOH (11 mL, 45% w/w). The solution, which became amber in
color, was allowed to warm to room temperature. The pH of the
solution dropped over time but was maintained above 9 with
additional NaOH (ca. 1 mL). The solution was refrigerated overnight
resulting in a final pH of 9. The solution was concentrated using a
rotary evaporator and dried under reduced pressure for 48 h to give
a light brown, amorphous solid. The basification procedure was
carried out in triplicate. The average dried weight of solid
product was 59.4 g.+-.0.82 g. Using this average value, the weight
of the crude solid potassium/sodium salts for the total organic
acid solution was calculated to be 653.4 g, 80.6% yield by
weight.
EXAMPLE 22
Isolation of Monopotassium Glucarate MPG from Diffusion Dialysis
Reclaimed Acid
[0071] A portion of the reclaimed nitric acid stock solution (40
mL, Example 16) was chilled in an ice bath and made basic with
aqueous KOH (35 mL, 45% by weight). The solution was allowed to
warm to room temperature and the pH was maintained above 9.5 with
additional KOH. After stirring at room temperature for 5 h, the
solution was cooled overnight. Crystals grew from the solution
during this time. The crystals were isolated by filtration, washed
with cold water (3.times.3 mL), and dried under reduced pressure to
give potassium nitrate as colorless needles (5.80 g). The filtrate
was chilled in an ice bath and back titrated to pH 3.7 with
concentrated HNO.sub.3 (8 mL). Precipitate formed when the pH of
the solution fell below 5. The mixture was cooled overnight then
the precipitate was isolated by filtration, washed with cold water
(3.times.5 mL), and dried under reduced pressure to give MPG as a
white powder (19.13 g). The weight of MPG for the total reclaimed
nitric acid solution was calculated to be 100.21 g, 0.3670 mol,
12.4% yield by weight.
EXAMPLE 23
Preparation of Sodium Potassium D-Glucarate from Monopotassium
D-Blucarate. Procedure 1. (Styron, 2002)
[0072] Aqueous sodium hydroxide solution (33 mL, 6 M) was added to
a slurry of monopotassium D-glucarate (50.0 g, 0.201 mol) in water
(150 mL) until all of the solid dissolved and a constant pH of 9.7
was reached. The solution was concentrated to a syrup and seeded
with the title compound. A solid crystalline cake formed over 24 h.
The crystals were isolated by filtration, washed with cold 1:1
ethanol/water (3.times.15 mL), and dried under reduced pressure to
give sodium potassium D-glucarate as colorless crystals (48.2 g,
0.157 mol as the dihydrate, 78.3%).
EXAMPLE 24
Preparation of Sodium Potassium D-Glucarate from Monopotassium
D-glucarate. Procedure 2. (Styron, 2002)
[0073] Aqueous sodium hydroxide solution (21 mL, 2 M) was added to
a slurry of monopotassium D-glucarate (10.0 g, 40.3 mmol) in water
(50 mL) until all of the solid dissolved and a constant pH of 10
was reached. The volume of the solution was reduced to 20 mL by
rotary evaporator. Methanol (15 mL) was added, producing a cloudy
solution which cleared upon heating. The solution was allowed to
sit undisturbed at 5.degree. C. Crystals grew from the solution
over a 48 h period. The crystals were isolated by filtration,
washed with cold 1:1 methanol/water (3.times.5 mL), and dried under
reduced pressure to give sodium potassium D-glucarate as colorless
crystals (10.2 g, 33.2 mmol as the dihydrate, 82.4%).
EXAMPLE 25
Preparation of Dipotassium D-Glucarate from Monopotassium
D-Glucarate. (Styron, 2002)
[0074] Aqueous potassium hydroxide solution (27 mL, 2 M) was added
to a slurry of monopotassium D-glucarate (10.2 g, 41.1 mmol) in
water (50 mL) until all of the solid dissolved and a constant pH of
10 was reached. The solution was concentrated to a syrup and seeded
with the title compound. Crystals grew slowly from the syrup. After
two weeks, the crystals were isolated by filtration, washed with
cold 1:1 ethanol/water (3.times.5 mL), and dried under reduced
pressure to give dipotassium D-glucarate as colorless crystals
(8.14 g, 26.8 mmol as the monohydrate, 65.1%).
[0075] It is understood that the foregoing examples are merely
illustrative of the present invention. Certain modifications of the
articles and/or methods employed may be made and still achieve the
objectives of the invention. Such modifications are contemplated as
within the scope of the claimed invention.
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References