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.

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 1 , 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.