Methods for forming peroxyformic acid and uses thereof

• US 10,233,149 B2
• Filed: 10/11/2017
• Issued: 03/19/2019
• Est. Priority Date: 12/18/2014
• Status: Active Grant

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Inventors: Balasubramanian, Ramakrishnan, Li, Junzhong, Staub, Richard, Keasler, Victor, Bennett, Brian, Brewster, Allison
• Primary Examiner(s): Bakshi, Pancham
• Assistant Examiner(s): Luderer, Mark R
• Application Number:
  US15/730,502
• Publication Number:
  US 20180093948A1
• Time in Patent Office: 524 Days
• CPC Class Codes: A01N 37/16 containing the group; Thio analogues thereof
• CPC Class Codes: A23L 3/34635 Antibiotics
• CPC Class Codes: A23L 3/3508 containing carboxyl groups
• CPC Class Codes: A23V 2002/00 Food compositions, function of food ingredients or processes for food or foodstuffs
• CPC Class Codes: C07C 407/00 Preparation of peroxy compounds
• CPC Class Codes: C07C 407/006 Stabilisation; Use of additives
• CPC Class Codes: C07C 409/24 the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
• CPC Class Codes: C23F 11/10 using organic inhibitors
• CPC Class Codes: C23F 11/141 Amines; Quaternary ammonium compounds
• CPC Class Codes: C23F 11/149 Heterocyclic compounds containing nitrogen as hetero atom
• CPC Class Codes: C23F 11/1673 Esters of phosphoric or thiophosphoric acids
• CPC Class Codes: Y02A 40/90 in food processing or handling, e.g. food conservation

Abstract

The present invention relates generally to methods for forming peroxyformic acid, comprising contacting formic acid with hydrogen peroxide. The methods for forming peroxyformic acid can include adding formic acid with a relatively lower concentration of hydrogen peroxide, or adding formic acid to a peroxycarboxylic acid composition or forming composition to react with hydrogen peroxide in the compositions. The present invention also relates to peroxyformic acid formed by the above methods. The present invention further relates to the uses of peroxyformic acid for treating a variety of targets, e.g., target water, including target water used in connection with oil- and gas-field operations. The present invention further relates to methods for reducing or removing H₂S or iron sulfide in the treated water source, improving clarity of the treated water source, or reducing the total dissolved oxygen or corrosion in the treated water source, using peroxyformic acid, including peroxyformic acid generated in situ.

Claims

1. A method for forming peroxyformic acid comprising:

contacting formic acid with hydrogen peroxide in the presence of at least 5 wt. % of an acid catalyst to form a resulting aqueous composition that comprises at least 7 wt. % of a peracid comprising peroxyformic acid within about 30 minutes.

2. The method of claim 1, wherein before the contacting, the formic acid is provided in a composition that comprises formic acid, the composition is an aqueous solution that comprises formic acid, or formic acid is provided in a composition that comprises a substance that generates formic acid upon contact with an aqueous composition.

3. The method of claim 1, wherein before the contacting, the hydrogen peroxide is provided in a composition that comprises hydrogen peroxide, the composition is an aqueous solution that comprises hydrogen peroxide, or the hydrogen peroxide is provided in a composition that comprises a substance that generates hydrogen peroxide upon contact with an aqueous composition.

4. The method of claim 1, wherein (a) the formic acid provided in a first aqueous composition is contacted with the hydrogen peroxide provided in a second aqueous composition to form peroxyformic acid in the resulting aqueous composition, wherein the acid catalyst is provided in the first aqueous composition or second aqueous composition;

or (b) the formic acid provided in a first aqueous composition is contacted with a substance that generates hydrogen peroxide upon contact with an aqueous composition provided in a second solid composition to form peroxyformic acid in the resulting aqueous composition wherein the acid catalyst is provided in the first aqueous composition or second solid composition.

5. The method of claim 1, wherein (a) a substance that generates formic acid upon contact with an aqueous composition provided in a first solid composition is contacted with hydrogen peroxide provided in a second aqueous composition to form peroxyformic acid in the resulting aqueous composition, wherein the acid catalyst is provided in the first solid composition or in the second aqueous composition;

(b) a substance that generates formic acid upon contact with an aqueous composition provided in a first solid composition and a substance that generates hydrogen peroxide upon contact with an aqueous composition provided in a second solid composition are contacted with a third aqueous composition to form peroxyformic acid in the resulting aqueous composition, wherein the acid catalyst is provided in the first solid composition, second solid composition, or third aqueous composition;

or (c) a substance that generates formic acid upon contact with an aqueous composition and a substance that generates hydrogen peroxide upon contact with an aqueous composition are provided in a first solid composition, and the first solid composition is contacted with a second aqueous composition to form peroxyformic acid in the resulting aqueous composition, wherein the acid catalyst is provided in the first solid composition or second aqueous composition.

6. The method of claim 4, wherein either the first or second composition further comprises a surfactant, enzyme, builder, chelating agent, additional catalyst, and/or additional functional ingredient.

7. The method of claim 1, wherein the formed aqueous composition comprises about 15% (w/w) or less hydrogen peroxide.

8. The method of claim 1, wherein the formic acid and hydrogen peroxide are contacted in the presence of a C₂-C₂₂ carboxylic acid and the peracid in the formed aqueous composition comprises peroxyformic acid and a C₂-C₂₂ percarboxylic acid.

9. The method of claim 8, wherein the C₂-C₂₂ carboxylic acid is acetic acid, octanoic acid and/or sulfonated oleic acid, and the peracid in the formed aqueous composition comprises peroxyformic acid and one or more of peroxyacetic acid, peroxyoctanoic acid and peroxysulfonated oleic acid.

10. The method of claim 1, which is conducted at a temperature ranging from about −

2°

C. to about 70°

C.

11. The method of claim 1, which is further conducted in the presence of an enzyme catalyst.

12. The method of claim 4, wherein before the contacting, the second aqueous composition comprises from about 1 (w/v) to about 40 (w/v) of the C₂-C₂₂ percarboxylic acid.

13. The method of claim 1, wherein the resulting aqueous composition further comprises a stabilizing agent for the peracid.

14. The method of claim 1, wherein the resulting aqueous composition comprises up to about 20% peroxyformic acid.

15. A peroxyformic acid composition formed by the method of claim 1.

16. A method for treating a target, which method comprises:

contacting a target with an effective amount of said peroxyformic acid composition of claim 15 to form a treated target composition,

wherein said treated target composition comprises from about 0.5 ppm to about 5,000 ppm of said peroxyformic acid, and said contacting lasts for sufficient time to stabilize or reduce microbial population in and/or on said target or said treated target composition, and

wherein the target is water in a fabric or textile application and the laundry or textile substrates, and the method comprises providing an effective amount of the peroxyformic acid composition to the water source and fabric or textile substrates in need of treatment.

17. The method of claim 16, wherein the water is a wash water and/or rinse water of a laundry machine to contact the fabric or textile substrates for a sufficient time to clean and reduce antimicrobial populations on the fabric or textile substrates and the water.

18. The method of claim 16, wherein the peroxyformic acid is used at a concentration from about 0.5 ppm to about 1,000 ppm.

19. The method of claim 16, wherein the contacting step lasts for at least 30 seconds and is conducted at a temperature ranging from about 0°

C. to about 70°

C.

20. The method claim 16, wherein the microbial population in and/or on the target or the treated target composition is reduced by at least one log₁₀.

21. The method of claim 16, further comprising a rinse step to remove any excess peroxyformic acid composition from the target.