SYSTEM AND METHOD FOR GENERATION OF REACTIVE OXYGEN SPECIES AND APPLICATIONS THEREOF

• US 20170107128A1
• Filed: 09/07/2013
• Published: 04/20/2017
• Est. Priority Date: 09/07/2012
• Status: Abandoned Application

• Current Assignee: Clean Chemistry Inc.
• Original Assignee: Clean Chemistry Inc.
• Inventors: Buschmann, Wayne
• Application Number:
  US15/308,966
• Publication Number:
  US 20170107128A1
• Time in Patent Office: Days
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 37/16 containing the group; Thio analogues thereof
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: A61L 2/0088 Liquid substances
• CPC Class Codes: A61L 2/18 Liquid substances or solutions comprising solids or dissolved gases
• CPC Class Codes: A61L 2/186 Peroxide solutions
• CPC Class Codes: A61L 2202/21 Pharmaceuticals, e.g. medicaments, artificial body parts
• CPC Class Codes: B09C 1/002 involving in-situ ground water treatment
• CPC Class Codes: B09C 1/08 chemically
• CPC Class Codes: B09C 2101/00 In situ
• CPC Class Codes: C01B 13/00 Oxygen; Ozone; Oxides or hydroxides in general
• CPC Class Codes: C01B 13/145 After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
• CPC Class Codes: C02F 1/4672 by electrooxydation
• CPC Class Codes: C02F 1/66 by neutralisation; pH adjustment for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 2103/002 Grey water, e.g. from clothes washers, showers or dishwashers
• CPC Class Codes: C02F 2103/007 Contaminated open waterways, rivers, lakes or ponds
• CPC Class Codes: C02F 2103/06 Contaminated groundwater or leachate
• CPC Class Codes: C02F 2103/10 from quarries or from mining activities
• CPC Class Codes: C02F 2303/04 Disinfection
• CPC Class Codes: C02F 2305/02 : Specific form of oxidant
• CPC Class Codes: C02F 2305/023 : Reactive oxygen species, singlet oxygen, OH radical
• CPC Class Codes: C07C 407/00 : Preparation of peroxy compounds
• CPC Class Codes: C07C 409/26 : Peracetic acid
• CPC Class Codes: C09K 2208/32 : Anticorrosion additives
• CPC Class Codes: C09K 8/524 : organic depositions, e.g. paraffins or asphaltenes
• CPC Class Codes: C09K 8/528 : inorganic depositions, e.g. sulfates or carbonates
• CPC Class Codes: C09K 8/54 : Compositions for in situ inhibition of corrosion in boreholes or wells
• CPC Class Codes: C11D 7/04 : Water-soluble compounds
• CPC Class Codes: C25B 1/30 : Peroxides
• CPC Class Codes: C25B 9/17 : Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
• CPC Class Codes: C25B 9/19 : with diaphragms
• CPC Class Codes: C25B 9/63 : Holders for electrodes; Positioning of the electrodes

Abstract

Reactive oxygen species formulations as well as methods for making and using such formulations. Reactive oxygen species formulations comprising one or more parent oxidants, such as peroxides, or peroxyacids, and one or more reactive oxygen species. (ROS). The formulations optionally contain in addition one or more reactive species other than ROS. The reactive oxygen species and other reactive species when present provide chemical reactivity, oxidative activity and/or antimicrobial activity not provided otherwise by the parent oxidant.

Claims

1. A method for generating a reactive oxygen species formulation, the method comprising:

generating an alkaline hydrogen peroxide solution;

mixing the alkaline hydrogen peroxide solution with an acyl donor such that a peracid concentrate is produced, wherein the peracid concentrate has minimal hydrogen peroxide residual;

adjusting the pH of the peracid concentrate to the activated pH range for generating the reactive oxygen species.

2. The method of claim 1 wherein the reactive oxygen species formulation is a singlet oxygen precursor formulation.

3. The method of claim 1 wherein the reactive oxygen species formulation comprises singlet oxygen and superoxide.

4. The method of claim 1 wherein the acyl donor is an acetyl donor.

5. The method of claim 1 wherein the alkaline hydrogen peroxide solution is generated from the combination of an alkali and a hydrogen peroxide concentrate or wherein the alkaline hydrogen peroxide solution is generated electrochemically.

6. The method of claim 5 wherein the reactive oxygen species formulation is a singlet oxygen precursor formulation.

7. The method of claim 5 wherein the reactive oxygen species formulation comprises singlet oxygen and superoxide.

8. The method of claim 5 wherein the acyl donor is an acetyl donor.

9. The method of any one of claims 1-8 wherein the hydrogen peroxide solution is generated using a molar ratio of H₂O₂ to alkali in the range 1:

1.2 to 1;

2.5

10. The method of any one of claims 1-8 wherein the peracid concentrate is produced by mixing the alkaline hydrogen peroxide solution with the acyl donor such that the molar ratio of hydrogen peroxide to acyl donor is in the range 1:

1.25 to 1;

4.

11. The method of any one of claims 1-8 further comprising the step of further activating the reactive oxygen species using activation chosen from a Fenton or Fenton-like catalyst, ultrasound, ultraviolet radiation or thermal activation.

12. The method of any one of claims 1-8 further comprising the step of further activating the reactive oxygen species using activation chosen from a Fenton or Fenton-like catalyst, ultrasound, ultraviolet radiation or thermal activation and wherein the reactive oxygen species formed in the further activation step is hydroxyl radical.

13. The method of any one of claims 1-8 further comprising storing the alkaline hydrogen peroxide in a holding tank for immediate or future use.

14. The method of any one of claims 1-8 further comprising the step of distributing the reactive oxygen species to its point of use, wherein the reactive oxygen species is distributed in at least one form chosen from the group consisting of:

the form of a liquid, an ice, a foam, an emulsion, a microemulsion and an aerosol; and

wherein the reactive oxygen species is applied to the point of use by an application chosen from the group consisting of;

injection, flooding, spraying, and circulation.

15. The method any one of claims 1-8 wherein the alkaline hydrogen peroxide concentrate is electrochemically generated, has a pH in the range of 12.0 to 13.0, and has a percent weight of hydrogen peroxide in the range of 0.1 to 3 wt %.

16. The method any one of claims 1-8 wherein the alkaline hydrogen peroxide concentrate is electrochemically generated, and the acid concentrate is co-generated during the step of electrochemically generating the alkaline hydrogen peroxide concentrate.

33. A method for oxidizing one or more environments or substrates which comprises contacting the one or more environments or substrates with a reactive oxygen species formulation of claim 23-25 or which is prepared by the method of any one of claims 1-8 or claims 26-30.

34. A method for oxidizing one or more environments or substrates which comprises contacting the one or more environments or substrates with a reactive oxygen species formulation of claim 23-25 or which is prepared by the method of any one of claims 1-8 or claims 26-30 which comprises:

cleaning in place of pipes, tanks and other processing equipment;

removal of contaminants from water including wastewater, greywater, raw water,

produced water or ground water;

denaturing or killing microorganisms;

soil decontamination or remediation;

hard surface cleaning or decontamination;

cleaning of membrane filtration systems;

flushing of well casings and water distribution pipes; and

in-situ chemical oxidation.

37. A method for treating waste water comprising:

which comprises contacting the one or more environments or substrates with a reactive oxygen species formulation of claim 23-25 or which is prepared by the method of any one of claims 1-8 or claims 26-30;

17. A reactive oxygen species precursor formulation comprising a peracid concentrate comprising a mixture of alkaline hydrogen peroxide and an acyl donor. wherein the precursor formulation is capable of generating singlet oxygen by the reaction of alkaline hydrogen peroxide and the acyl donor;

the precursor formulation having minimal hydrogen peroxide residual to minimize quenching of singlet oxygen, and the precursor formulation having a pH between 6.5 and 12.5.

18. The reactive oxygen species precursor formulation of claim 17 wherein the molar ratio of hydrogen peroxide to acetyl donor reactive groups is in the range 1:

1.25 to 1;

4.

19. The reactive oxygen species precursor formulation of claim 17 further comprising superoxide.

20. The reactive oxygen species precursor formulation of claim 19 wherein the initial molar ratio of superoxide to peracid ranges from 5:

1 to 3;

1.

21. The reactive oxygen species precursor formulation of claim 19 wherein the initial molar ratio of superoxide to peracid ranges from 3:

1 to 0.7 to 1.

22. The reactive oxygen species precursor formulation of any one of claims 17-21 wherein the initial pH ranges from 6.0 to 9.5.

23. A singlet oxygen formulation prepared by reacting the precursor formulation of any one of claims 17-21 with an acid concentrate resulting in formation of both peracetic acid and peracetic acid anion,

24. The reactive oxygen species of claim 23 exhibiting an ORP of 600 mv vs SHE or more.

25. The reactive oxygen species of claim 23 exhibiting an ORP of 700 mv vs SHE or more.

32. The superoxide formulation of claim 21 wherein the pH is 12-13.

26. A method for generating a superoxide formulation comprising:

electrochemically generating a solution containing a mixture of superoxide and peroxide wherein the molar ratio of superoxide to hydrogen peroxide co-generated ranges from 0.01;

1 to 10;

1 and the pH ranges from 8 to 13.

27. The method of claim 26 wherein an acid concentrate is co-generated during the step of electrochemically generating a superoxide solution and the method further comprises a step of adjusting the pH of electrochemically generated solution with the co-generated acid.

28. The method of claim 26 further comprising a step of diluting the superoxide solution to near point of use concentration.

29. The method of claim 26 wherein the electrochemically generated solution contains hydroperoxyl radicals or hydroxyl radicals.

30. The method of claim 26 further comprising the step of further activating the electrochemically generated solution using activation chosen from a Fenton or Fenton-like catalyst, ultrasound, ultraviolet radiation and thermal activation, to produce a radical species.

31. A superoxide formulation prepared by electrochemically generating a mixture of superoxide and hydrogen peroxide wherein the molar ratio of superoxide to hydrogen peroxide co-generated ranges from 0.01:

1 to 10;

1 and the pH is 8-13.

35. A method for oxidizing one or more substances in an environment which comprises contacting the one or more substances with a formulation comprising superoxide and singlet oxygen.

36. The method of claim 35 which comprises:

cleaning in place of pipes, tanks and other processing equipment;

removal of contaminants from water including wastewater, greywater, raw water, produced water or ground water;

soil decontamination or remediation;

hard surface cleaning or decontamination;

cleaning of membrane filtration systems;

flushing of well casings and water distribution pipes; and

in-situ chemical oxidation.

38. A method for treating waste water comprising:

electrochemically co-generating a cathode output solution comprising superoxide and hydrogen peroxide;

mixing the cathode output solution into a waste water source; and

optionally

adjusting the pH of the cathode output solution before the step of mixing the cathode output solution into a waste water source.