System and method for generation of point of use reactive oxygen species

• US 9,517,956 B2
• Filed: 07/11/2016
• Issued: 12/13/2016
• Est. Priority Date: 09/07/2012
• Status: Active Grant

• Current Assignee: Clean Chemistry Inc.
• Original Assignee: Clean Chemistry, LLC
• Inventors: Buschmann, Wayne
• Primary Examiner(s): ANTHONY, JOSEPH DAVID
• Application Number:
  US15/206,901
• Publication Number:
  US 20160318778A1
• Time in Patent Office: 155 Days
• Field of Search: None
• US Class Current: 1/1
• 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

Systems and methods for generating reactive oxygen species formulations useful in various oxidation applications. Exemplary formulations include singlet oxygen or superoxide and can also contain hydroxyl radicals or hydroperoxy radicals, among others. Formulations can contain other reactive species, including other radicals. Exemplary formulations containing peracids are activated to generate singlet oxygen. Exemplary formulations include those containing a mixture of superoxide and hydrogen peroxide. Exemplary formulations include those in which one or more components of the formulation are generated electrochemically. Formulations of the invention containing reactive oxygen species can be further activated to generate reactive oxygen species using activation chosen from a Fenton or Fenton-like catalyst, ultrasound, ultraviolet radiation or thermal activation. Exemplary applications of the formulations of the invention among others include: cleaning in place applications, water treatment, soil decontamination and flushing of well casings and water distribution pipes.

Claims

1. A reactive oxygen species precursor formulation comprising a peracid concentrate capable of generating singlet oxygen, the peracid concentrate comprising a mixture of an alkaline concentrate, hydrogen peroxide and an acyl donor, wherein the molar ratio of hydrogen peroxide to acyl donor reactive groups is in the range of about 1:

1.25 to about 1;

4, and wherein the reactive oxygen species precursor formulation has a pH value ranging from about pH 9.5 to about pH 12.5 and a peracid anion to peracid molar ratio greater than about 1;

1, and wherein the peracid concentrate has a minimal hydrogen peroxide residual to minimize quenching of singlet oxygen.

2. The reactive oxygen species precursor formulation of claim 1, wherein the reactive oxygen species precursor formulation undergoes the following chemical reaction:

AcOOH+AcOO⁻

→

¹O₂+AcOH+AcO⁻

.

3. The reactive oxygen species precursor formulation of claim 1, wherein the reactive oxygen species precursor formulation is a singlet oxygen precursor formulation.

4. The reactive oxygen species precursor formulation of claim 1, wherein the acyl donor is an acetyl donor.

5. The reactive oxygen species precursor formulation of claim 1, wherein the acyl donor is one of an oxygen-acyl or oxygen-acetyl donor or a nitrogen-acyl or nitrogen-acetyl donor.

6. The reactive oxygen species precursor formulation of claim 1, wherein the peracid concentrate has minimal hydrogen peroxide residual.

7. The reactive oxygen species precursor formulation of claim 1, wherein the peracid concentrate has a molar ratio of peracetic acid to hydrogen peroxide of at least about 32:

1.

8. A method for oxidizing a contaminant, comprising:

contacting a reactive oxygen precursor formulation with an aqueous stream containing the contaminant, wherein the reactive oxygen precursor formulation comprises;

a peracid concentrate capable of generating singlet oxygen, the peracid concentrate comprising a mixture of an alkaline concentrate, hydrogen peroxide and an acyl donor, wherein the molar ratio of hydrogen peroxide to acyl donor reactive groups is in the range of about 1;

1.25 to about 1;

4, and wherein the reactive oxygen species precursor formulation has a pH value ranging from about pH 9.5 to about pH 12.5 and a peracid anion to peracid molar ratio greater than about 1;

1, and wherein the peracid concentrate has a minimal hydrogen peroxide residual to minimize quenching of singlet oxygen;

wherein the contacting of the reactive oxygen precursor formulation with the aqueous stream generates a reactive oxygen species and oxidizes the contaminant.

9. The method of claim 8, wherein the aqueous stream is one of a hydraulic fracturing water or produced water from a subsurface formation.

10. The method of claim 8, wherein the contaminant is one or more of an organic material, inorganic materials, metals, suspended solids, silt, petrochemical, bacteria, slime, and microbes.

11. The method of claim 8, wherein the reactive oxygen precursor formulation is a singlet oxygen precursor formulation.

12. The method of claim 8, wherein the reactive oxygen precursor formulation has a molar ratio of peracetic acid to hydrogen peroxide of at least about 32:

1.

13. A method for oxidizing a contaminant, comprising:

contacting a reactive oxygen precursor formulation with one of a hydraulic fracturing water, a produced water from a subsurface formation or an oil and/or gas production well water containing the contaminant, wherein the reactive oxygen precursor formulation comprises;

a peracetate concentrate capable of generating singlet oxygen, the peracetate concentrate comprising a mixture of an alkaline concentrate, hydrogen peroxide and an acyl donor, wherein the molar ratio of hydrogen peroxide to acyl donor reactive groups is in the range of about 1;

1.25 to about 1;

4, and wherein the reactive oxygen species precursor formulation has a pH value ranging from about pH 9.5 to about pH 12.5 and a peracetate anion to peracetic molar ratio greater than about 1;

1, and wherein the peracetate concentrate has a minimal hydrogen peroxide residual to minimize quenching of singlet oxygen;

wherein the contacting of the reactive oxygen precursor formulation with the one of the hydraulic fracturing water, the produced water from a subsurface formation or the oil and/or gas production well water generates an oxygen species and oxidizes the contaminant.

14. The method of claim 13, wherein the contaminant is one or more of an organic material, inorganic materials, metals, suspended solids, silt, petrochemical, bacteria, slime, and microbes.

15. The method of claim 13, wherein the reactive oxygen precursor formulation is a singlet oxygen precursor formulation.

16. The method of claim 13, wherein the reactive oxygen precursor formulation has a molar ratio of peracetic acid to hydrogen peroxide of at least about 32:

1.