IP Library Granted Patent US 12,382,955
Granted Patent B2
US 12,382,955 · App. 18/755,130 · Granted Aug 12, 2025

Peroxyformic acid compositions for membrane filtration cleaning in energy services

Inventors: Junzhong Li (Saint Paul, MN); Cynthia Bunders (Saint Paul, MN); Richard Staub (Saint Paul, MN); Paul Frazer Schacht (Saint Paul, MN); Caleb Power (Saint Paul, MN); Ramakrishnan Balasubramanian (Saint Paul, MN); Robert J. Ryther (Saint Paul, MN); Catherine Hanson (Saint Paul, MN)
Assignee: ECOLAB USA INC.
A01N37/16A61L2/18A61L2/186A61L2202/17
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,382,955
App. No.
18/755,130
Granted
Aug 12, 2025
Kind
B2
Abstract

Peroxyformic acid compositions for treatment and removal of biofilm growth and mineral deposits on membranes for energy services applications are disclosed. In particular, peroxyformic acid compositions are generated in situ or on site generation for the reduction and prevention, of biofilms and the mitigation of mineral buildup on the membranes. The compositions according to the invention are compatible with the membranes under application of use conditions.

Claims (21)

1. A method for treating a membrane system to reduce biofilm growth and mineral deposits to prevent fouling of said membrane system comprising:

contacting the fouled membrane with a peroxyformic acid composition for at least 15 minutes to 15 hours, wherein the peroxyformic acid composition is biodegradable, membrane compatible, and does not damage the membrane as measured by a decrease in flux of the membrane; and

contacting the fouled membrane with one or more additional treatments comprising an acidic treatment, an alkaline treatment, an enzymatic treatment and/or a neutral treatment either before or after the peroxyformic acid composition contacts the membrane; and

reducing biofilm growth and/or mineral deposits, wherein the contacting occurs not more frequently than once every 24 hours and is intermittent and occurs daily, bi-weekly, or weekly at a frequency sufficient to reduce biofilm growth and/or mineral deposits on the membrane to prevent fouling.

2. The method of claim 1 , wherein the membrane is a reverse osmosis membrane, nanofiltration membrane, ultrafiltration membrane, or a microfiltration membrane.

3. The method of claim 1 , wherein the membrane comprises cellulose, cellulose acetate, nitrocellulose, polysulfone, polyethersulfone, fully aromatic polyamide, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylnitrile, polypropylene, carbon, alpha-aluminum oxide, zirconium oxide, ceramic and/or stainless steel.

4. The method of claim 1 , wherein the contacting with the peroxyformic acid composition does not negatively impact the pressure on the membrane and/or decrease the lifespan of the membrane in comparison to a membrane treated with other oxidizer chemistries.

5. The method of claim 1 , further comprising at least one additional step of a first product removal step before the membrane is contacted with the peroxyformic acid composition, a pre-rinse step of washing the membrane with water, and/or a soak step of washing the membrane.

6. The method of claim 1 , wherein the membrane is contacted with from about 0.00001% to about 0.1% active peroxyformic acid.

7. The method of claim 1 , wherein the membrane is contacted with peroxyformic acid for at least 1 hour.

8. The method of claim 1 , wherein the membrane is contacted with an additional peroxyacid, chelants, solvent, surfactant and/or other additives which may be dosed separately or simultaneously with the peroxyformic acid composition.

9. The method of claim 1 , wherein the membrane is contacted with the peroxyformic acid composition at temperature range from ambient temperature to about 60° C.

10. The method of claim 1 , wherein the peroxyformic acid composition is generated in situ by contacting formic acid with hydrogen peroxide, 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 2 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 2 or higher within about 1 hour of said contacting.

11. The method of claim 10 , wherein the formic acid is provided in a first aqueous composition and is contacted with a second aqueous solution of the hydrogen peroxide.

12. The method of claim 10 , wherein the contacting of the formic acid and hydrogen peroxide is conducted in the presence of an acid catalyst.

13. The method of claim 1 , wherein the peroxyformic acid composition comprises a wetting agent, a chelant, solvent and/or a surfactant.

14. The method of claim 1 , wherein the ratio of the peroxyformic acid to the hydrogen peroxide in the peroxyformic acid composition is from about 10:1 to about 40:1.

15. The method of claim 1 , wherein the ratio of the peroxyformic acid to the hydrogen peroxide in the peroxyformic acid composition is from about 25:1 to about 40:1.

16. The method of claim 1 , which further comprises a step of reducing the concentration of the hydrogen peroxide in the peroxyformic acid composition.

17. The method of claim 1 , wherein contacting the membrane with at least about 1 ppm to about 300 ppm actives of peroxyformic acid composition.

18. The method of claim 1 , wherein contacting the membrane with at least about 1 ppm to about 200 ppm actives of peroxyformic acid composition.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 27, 2024
From: LI, JUNZHONG; BUNDERS, CYNTHIA; STAUB, RICHARD; SCHACHT, PAUL FRAZIER; POWER, CALEB; BALASUBRAMANIAN, RAMAKRISHNAN; RYTHER, ROBERT J.; HANSON, CATHERINE
To: ECOLAB USA INC.
Reel/Frame 067854/0770 →
Continuity (6)
Continuation 18297482 · Apr 7, 2023
Continuation 17302678 · May 10, 2021
Continuation 16559894 · Sep 4, 2019
Continuation 15623024 · Jun 14, 2017
Provisional Application 62434981 · Dec 15, 2016
Related Publication 20240341306A1 · Oct 17, 2024
References Cited (109)
US 5616335A · Nicolle et al. · 1997 [cited by applicant]
US 6139756A · Fuchs et al. · 2000 [cited by applicant]
US 6211237B1 · Huss et al. · 2001 [cited by applicant]
US 6254801B1 · Reinold et al. · 2001 [cited by applicant]
US 6284719B1 · Simms · 2001 [cited by applicant]
US 6468472B1 · Yu et al. · 2002 [cited by applicant]
US 7638067B2 · Hilgren et al. · 2009 [cited by applicant]
US 7915445B2 · Maatta et al. · 2011 [cited by applicant]
US 8802061B2 · Tichy et al. · 2014 [cited by applicant]
US 8828910B2 · Aksela et al. · 2014 [cited by applicant]
US 8877354B2 · Horiuchi et al. · 2014 [cited by applicant]
US 9044403B2 · Shultz · 2015 [cited by applicant]
US 9192909B2 · Kraus et al. · 2015 [cited by applicant]
US 9617170B2 · Karpova et al. · 2017 [cited by applicant]
US 10278392B2 · Bolduc et al. · 2019 [cited by applicant]
US 10457850B2 · Sun et al. · 2019 [cited by applicant]
US 11241009B2 · Bolduc et al. · 2022 [cited by applicant]
US 11241658B2 · Schacht et al. · 2022 [cited by applicant]
US 11882826B2 · Bolduc et al. · 2024 [cited by applicant]
US 20020177732A1 · Pohjanvesi et al. · 2002 [cited by applicant]
US 20040143133A1 · Smith et al. · 2004 [cited by applicant]
US 20050072743A1 · Schneider et al. · 2005 [cited by applicant]
US 20060177518A1 · Stevenson et al. · 2006 [cited by applicant]
US 20070023363A1 · Daines et al. · 2007 [cited by applicant]
US 20070056904A1 · Hogt et al. · 2007 [cited by applicant]
US 20070249712A1 · Dee et al. · 2007 [cited by applicant]
US 20080095677A1 · McSherry et al. · 2008 [cited by applicant]
US 20090200234A1 · Schacht et al. · 2009 [cited by applicant]
US 20090221704A1 · Aksela et al. · 2009 [cited by applicant]
US 20090320214A1 · Shamayeli et al. · 2009 [cited by applicant]
US 20100084340A1 · Monsrud et al. · 2010 [cited by applicant]
US 20110094044A1 · Shamayeli et al. · 2011 [cited by applicant]
US 20120228221A1 · Kakigami et al. · 2012 [cited by applicant]
US 20130079733A1 · Burt et al. · 2013 [cited by applicant]
US 20130203849A1 · Ben Yehuda · 2013 [cited by applicant]
US 20140039050A1 · da Costa et al. · 2014 [cited by applicant]
US 20140097144A1 · Li et al. · 2014 [cited by applicant]
US 20140124461A1 · Buisson et al. · 2014 [cited by applicant]
US 20140274857A1 · Schacht et al. · 2014 [cited by applicant]
US 20140367334A1 · Salonen et al. · 2014 [cited by applicant]
US 20150018319A1 · Larson et al. · 2015 [cited by applicant]
US 20150056679A1 · Patten et al. · 2015 [cited by applicant]
US 20150183673A1 · Musale et al. · 2015 [cited by applicant]
US 20150240328A1 · Urbani · 2015 [cited by applicant]
US 20150351383A1 · Kolari et al. · 2015 [cited by applicant]
US 20150351389A1 · Kolari et al. · 2015 [cited by applicant]
US 20160068417A1 · Buschmann · 2016 [cited by applicant]
US 20160176814A1 · Balasubramanian et al. · 2016 [cited by applicant]
AU 2007311532A1 · 2008 [cited by applicant]
CA 2475361A1 · 2003 [cited by applicant]
CA 3009259A1 · 2017 [cited by applicant]
CN 101054779B · 2012 [cited by applicant]
CN 102876287B · 2014 [cited by applicant]
CN 104206413A · 2014 [cited by applicant]
CN 107925112A · 2018 [cited by applicant]
DE 3504394A1 · 1985 [cited by applicant]
EP 0231632A2 · 1987 [cited by applicant]
EP 0231632A3 · 1987 [cited by applicant]
EP 1022946B1 · 2000 [cited by applicant]
EP 1247802A1 · 2002 [cited by applicant]
EP 1125497A2 · 2003 [cited by applicant]
EP 1244842B1 · 2004 [cited by applicant]
EP 1131016B1 · 2005 [cited by applicant]
EP 2609990A1 · 2013 [cited by applicant]
EP 2653448B1 · 2018 [cited by applicant]
EP 3169844B1 · 2018 [cited by applicant]
FI 113056B · 1999 [cited by applicant]
FI 126082B · 2014 [cited by applicant]
JP 60175504A · 1985 [cited by applicant]
JP 2000117069A · 2000 [cited by applicant]
JP 2005154551A · 2005 [cited by applicant]
JP 2008100161A · 2008 [cited by applicant]
WO 9517241A1 · 1995 [cited by applicant]
WO 9623858A1 · 1996 [cited by applicant]
WO 9719594A1 · 1997 [cited by applicant]
WO 9856988A1 · 1998 [cited by applicant]
WO 9946234A1 · 1999 [cited by applicant]
WO 2000045639A1 · 2000 [cited by applicant]
WO 0170030A2 · 2001 [cited by applicant]
WO 0170030A3 · 2001 [cited by applicant]
WO 03092919A1 · 2003 [cited by applicant]
WO 2005005028A1 · 2005 [cited by applicant]
WO 2007031596A2 · 2007 [cited by applicant]
WO 2008056025A3 · 2008 [cited by applicant]
WO 2008088873A1 · 2008 [cited by applicant]
WO 2008120509A1 · 2008 [cited by applicant]
WO 2012025943A1 · 2012 [cited by applicant]
WO 2012177366A3 · 2012 [cited by applicant]
WO 2013051013A2 · 2013 [cited by applicant]
WO 2013098478A2 · 2013 [cited by applicant]
WO 2013098479A1 · 2013 [cited by applicant]
WO 20130175062A1 · 2013 [cited by applicant]
WO 2013184605A1 · 2013 [cited by applicant]
WO 2014062487A1 · 2014 [cited by applicant]
WO 2014154946A1 · 2014 [cited by applicant]
WO 2017106623A1 · 2017 [cited by applicant]
WO 2017194842A1 · 2017 [cited by applicant]
WO 2018091784A1 · 2018 [cited by applicant]
Chhetri et al. Chemical disinfection of combined sewer overflow waters using performic acid or peracetic acids. Science of the Total Environment. Aug. 15, 2014;490:1065-72. [cited by applicant]
Maeda Y. Roles of sulfites in reverse osmosis (RO) plants and adverse effects in RO operation. Membranes. Jan. 31, 2022; 12(2):59 pages. [cited by applicant]
Soice et al. Studies of oxidative degradation in polyamide RO membrane barrier layers using pendant drop mechanical analysis. Journal of membrane science. Nov. 1, 2004;243(1-2):345-55. [cited by applicant]
Johnson, Greg, et al. “Kinetics of Mineral Scale Membrane Fouling” Technical Article, 14 pages, accessed from www.vsep.com as of Dec. 1, 2016. [cited by applicant]
Vance, Frederick W., et al. “New Solution for Controlling of Organic and BioFouling in High Pressure Membrane Applications” AMTA/AWWA Membrane Technology Conference & Exposition 2013, San Antonio, Texas, Feb. 25-28, 201… [cited by applicant]
Dejong, Robert L., “Atmospheric Corrosion Problems in Secondary Fibre Plants”, Enzyme Microb. Technol. (Jul. 1979) vol. 1, p. 205-209. [cited by applicant]
Littlejohn, et al., “Removal of NOx and SO2 from Flue Gas by Peracid Solutions”, Ind. Eng. Chem. Res. (1990) 29, pp. 1420-1424. [cited by applicant]
Ecolab USA Inc., PCT/US2017/037467 filed Jun. 14, 2017, “Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, or the Declaration”, mailed Sep. … [cited by applicant]
Ecolab USA, Inc., PCT/US2017/027622 filed Apr. 15, 2016, “International Search Report”, mailed Jul. 27, 2016. [cited by applicant]
Ecolab USA Inc., PCT/US2016/067139 filed Dec. 16, 2016, “The International Search Report and the Written Opinion of the International Searching Authority, or the Declaration”, mailed Jun. 1, 2017. [cited by applicant]
European Patent Office, “Extended European Search Report”, in connection with PCT/US2016/067139 filed Dec. 16, 2016, 8 pages, mailed Jun. 28, 2019. [cited by applicant]