Methods for forming peroxyformic acid and uses thereof

Patent metadata

Field	Value
Publication number	US-9845290-B2
Application number	US-201514972308-A
Country	US
Kind code	B2
Filing date	Dec 17, 2015
Priority date	Dec 18, 2014
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

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 H 2 S 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.

First claim

What is claimed is:

1. A method for forming peroxyformic acid comprising:
contacting a formic acid source with a hydrogen peroxide source to form a resulting aqueous composition comprising a peracid that comprises peroxyformic acid, and from about 0.0001 wt-% to about 20 wt-% of a corrosion inhibitor;
wherein the contacting is conducted in the presence of a mineral acid catalyst, and
wherein before said contacting, the ratio between the concentration of said formic acid source (w/v) and the concentration of said hydrogen peroxide source (w/v) is at least about 4 or higher, and the ratio between the concentration of said peracid (w/w) and the concentration of hydrogen peroxide source (w/w) in said formed resulting aqueous composition reaches at least about 4 or higher within about 1 hour of said contacting.

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

3. The method of claim 2 , wherein before the contacting, the composition is an aqueous solution that comprises formic acid.

4. The method of claim 2 , wherein the substance is a salt of formate or an ester of formate.

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

6. The method of claim 3 , wherein before the contacting, the composition is an aqueous solution that comprises hydrogen peroxide.

7. The method of claim 5 , wherein the substance comprises a precursor of hydrogen peroxide comprising sodium percarbonate, sodium perborate, urea hydrogen peroxide, PVP-hydrogen peroxide, or combinations thereof.

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

9. The method of claim 1 , wherein the amount of corrosion inhibitor in the resulting aqueous composition is from about 0.0001 wt-% to about 10 wt-%.

10. The method of claim 9 , wherein the corrosion inhibitor comprises a phosphate ester, a derivative of the phosphate ester, trimeric C19 unsaturated fatty acid, a quat amine, a derivative of the quat amine, an imidazoline, a derivative of the imidazoline, an alkyl pyridine, a derivative of the alkyl pyridine, a phosphonium salt or a derivative of the phosphonium salt.

11. The method of claim 1 , wherein a formic acid source 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.

12. The method of claim 1 , wherein the formic acid source provided in a first solid composition and the hydrogen peroxide source provided in a second solid composition are contacted with a third aqueous composition to form peroxyformic acid in the resulting aqueous composition.

13. The method of claim 1 , wherein the formic acid source and the hydrogen peroxide source 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.

14. The method of claim 1 , wherein before the contacting, the ratio between the concentration of the formic acid source (w/v) and the concentration of the hydrogen peroxide source (w/v) is from about 100 to about 4, and wherein the ratio between the concentration of the peracid (w/w) and the concentration of hydrogen peroxide source (w/w) in the formed aqueous composition reaches from about 1500 to about 4 within about 1 hour of the contacting.

15. The method of claim 1 , wherein the ratio between the concentration of the peracid (w/w) and the concentration of hydrogen peroxide (w/w) in the formed aqueous composition reaches from about 5 to about 40 within about 30 minutes of the contacting.

16. The method of claim/9, wherein the formed aqueous composition comprises about 5% (w/w) or less hydrogen peroxide.

17. The method of claim 3 , wherein the formic acid and the hydrogen peroxide are contacted in the absence of a C 2 -C 22 carboxylic acid and a C 2 -C 22 percarboxylic acid and the peracid in the formed aqueous composition comprises peroxyformic acid only.

18. The method of claim 1 , wherein the formic acid and hydrogen peroxide are contacted in the presence of a C 2 -C 22 carboxylic acid and the peracid in the formed aqueous composition comprises peroxyformic acid and the C 2 -C 22 percarboxylic acid.

19. The method of claim 1 , which is conducted at a temperature ranging from about −2° C. to about 70° C.

20. The method of claim 1 , wherein the mineral acid catalyst comprises sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid or combinations thereof.

21. The method of claim 1 , which is conducted in the presence of a cation acid exchange resin system.

22. The method of claim 1 , wherein the resulting aqueous composition comprises a stabilizing agent, wherein the stabilizing agent is a phosphonate salt(s) and/or a heterocyclic dicarboxylic acid.

23. The method of claim 1 , which further comprises a step of reducing the concentration of the hydrogen peroxide in the resulting aqueous composition.

24. The method of claim 23 , wherein the concentration of the hydrogen peroxide in the resulting aqueous composition is reduced using a catalase or a peroxidase.

25. The method of claim 1 , which is used to generate peroxyformic acid in situ for the application of the formed peroxyformic acid.

26. A peroxyformic acid composition formed by the method comprising:
contacting formic acid with hydrogen peroxide to form a resulting aqueous composition comprising a peracid that comprises peroxyformic acid, and from about 0.0001 wt-% to about 20 wt-% of a corrosion inhibitor;
wherein the contacting is conducted in the presence of a mineral acid catalyst, and
wherein before said contacting, the ratio between the concentration of said formic acid (w/v) and the concentration of said hydrogen peroxide (w/v) is about 4 or higher, and the ratio between the concentration of said peracid (w/w) and the concentration of hydrogen peroxide (w/w) in said formed resulting aqueous composition reaches about 4 or higher at least within 1 hour of said contacting.

27. The peroxyformic acid composition of claim 26 , wherein the amount of corrosion inhibitor in the resulting aqueous composition is from about 0.0001 wt-% to about 10 wt-%.

28. The peroxyformic acid composition of claim 27 , wherein the corrosion inhibitor comprises a phosphate ester, a derivative of the phosphate ester, trimeric C19 unsaturated fatty acid, a quat amine, a derivative of the quat amine, an imidazoline, a derivative of the imidazoline, an alkyl pyridine, a derivative of the alkyl pyridine, a phosphonium salt, a derivative of the phosphonium salt or combinations thereof.

29. The peroxyformic acid composition of claim 2

Assignees

• Ecolab Usa Inc

Inventors

• Balasubramanian Ramakrishnan
• Li Junzhong
• Staub Richard
• Keasler Victor
• Bennett Brian
• Brewster Allison

Classifications

• C23F11/1673

  Esters of phosphoric or thiophosphoric acids · CPC title

• C23F11/10

  using organic inhibitors · CPC title

• C07C409/24 Primary

  the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids · CPC title

• C23F11/141

  Amines; Quaternary ammonium compounds · CPC title

• A23V2002/00

  Food compositions, function of food ingredients or processes for food or foodstuffs · CPC title