METHODS FOR FORMING PEROXYFORMIC ACID AND USES THEREOF

• US 20160176814A1
• Filed: 12/17/2015
• Published: 06/23/2016
• 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, KEASLER, VICTOR, BENNETT, BRIAN, LI, JUNZHONG, STAUB, RICHARD, BREWSTER, ALLISON
• Granted Patent: US 9,845,290 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• 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

1-148. -148. (canceled)

149. :

A method for forming peroxyformic acid comprising;

contacting formic acid with hydrogen peroxide to form a resulting aqueous composition comprising a peracid that comprises peroxyformic acid,

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 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 4 hours of said contacting.

150. :

The method of claim 149, wherein before the contacting, the formic acid is provided in a composition that comprises formic acid or a substance that generates formic acid upon contact with an aqueous composition.

151. :

The method of claim 150, wherein before the contacting, the composition is an aqueous solution that comprises formic acid.

152. :

The method of claim 150, wherein the substance is a salt of formate or an ester of formate.

153. :

The method of claim 149, wherein before the contacting, the hydrogen peroxide is provided in a composition that comprises hydrogen peroxide or a substance that generates hydrogen peroxide upon contact with an aqueous composition.

154. :

The method of claim 153, wherein before the contacting, the composition is an aqueous solution that comprises hydrogen peroxide.

155. :

The method of claim 153, wherein the substance comprises a precursor of hydrogen peroxide comprising sodium percarbonate, sodium perborate, urea hydrogen peroxide, PVP-hydrogen peroxide, or combinations thereof.

156. :

The method of claim 149, 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.

157. :

The method of claim 149, wherein either the first or second composition further comprises a corrosion inhibitor, and wherein the amount of corrosion inhibitor in the resulting aqueous composition is from about 0.0001 wt-% to about 20 wt-%.

158. :

The method of claim 157, wherein the corrosion inhibitor comprises a phosphate ester, a derivative of the phosphate ester, a diacid, a derivative of the diacid, 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.

159. :

The method of claim 149, wherein 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.

160. :

The method of claim 149, wherein 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.

161. :

The method of claim 149, wherein 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.

162. :

The method of claim 149, wherein before the contacting, the ratio between the concentration of the formic acid (w/v) and the concentration of the hydrogen peroxide (w/v) is from about 100 to about 2, and 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 1500 to about 2 within about 2 hours of the contacting.

163. :

The method of claim 149, 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.

164. :

The method of claim 149, wherein the formed aqueous composition comprises about 5% (w/w) or less hydrogen peroxide.

165. :

The method of claim 149, wherein the formic acid and the hydrogen peroxide are contacted in the absence of a C₂-C₂₂ carboxylic acid and a C₂-C₂₂ percarboxylic acid and the peracid in the formed aqueous composition comprises peroxyformic acid only.

166. :

The method of claim 149, 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 the C₂-C₂₂ percarboxylic acid.

167. :

The method of claim 149, which is conducted at a temperature ranging from about 2°

C. to about 70°

C.

168. :

The method of claim 149, wherein the mineral acid catalyst comprises sulfuric acid, methanesulfonic acid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid or combinations thereof.

169. :

The method of claim 149, which is conducted in the presence of a cation acid exchange resin system.

170. :

The method of claim 149, wherein the resulting aqueous composition comprises a stabilizing agent, wherein the stabilizing agent is a phosphonate salt(s) and/or a heterocyclic dicarboxylic acid.

171. :

The method of claim 149, which further comprises a step of reducing the concentration of the hydrogen peroxide in the resulting aqueous composition.

172. :

The method of claim 171, wherein the concentration of the hydrogen peroxide in the resulting aqueous composition is reduced using a catalase or a peroxidase.

173. :

The method of claim 149, which is used to generate peroxyformic acid in situ for the application of the formed peroxyformic acid.

174. :

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,

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 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 at least within 4 hours of said contacting.

175. :

The method of claim 174, wherein either the formic acid provided as a first composition or the hydrogen peroxide provided as a second composition further comprises a corrosion inhibitor, and wherein the amount of corrosion inhibitor in the resulting aqueous composition is from about 0.0001 wt-% to about 10 wt.-%.

176. :

The method of claim 175, wherein the corrosion inhibitor comprises a phosphate ester, a derivative of the phosphate ester, a diacid, a derivative of the diacid, 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.

177. :

The peroxyformic acid composition of claim 174, wherein before the contacting, the ratio between the concentration of the formic acid (w/v) and the concentration of the hydrogen peroxide (w/v) is from about 100 to about 2, and 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 1500 to about 2 within about 2 hours of the contacting.

178. :

The peroxyformic acid composition of claim 174, wherein the resulting aqueous composition comprises from about 0.001% to about 20% peroxyformic acid, and about 5% (w/w) or less hydrogen peroxide.

179. :

The peroxyformic acid composition of claim 174, wherein the formic acid and the hydrogen peroxide are contacted in the absence of a C₂-C₂₂ carboxylic acid and a C₂-C₂₂ percarboxylic acid and the peracid in the formed aqueous composition comprises peroxyformic acid only.

180. :

The peroxyformic acid composition of claim 174, 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 the C₂-C₂₂ percarboxylic acid.

181. :

The peroxyformic acid composition of claim 174, wherein the resulting aqueous composition comprises a stabilizing agent, wherein the stabilizing agent is a phosphonate salt(s) and/or a heterocyclic dicarboxylic acid.

182. :

A method for treating a target with a peroxyformic acid composition comprising;

contacting a target with an effective amount of peroxyformic acid composition to form a treated target composition, wherein said treated target composition comprises from about 0.1 ppm to about 5,000 ppm of said peroxyformic acid, and said contacting lasts for sufficient time to stabilize or reduce microbial population by at least a 2 log reduction in and/or on said target or said treated target composition.

183. :

The method of claim 182, wherein said peroxyformic acid composition is generated in situ by the method comprising contacting formic acid with hydrogen peroxide to form a resulting aqueous composition comprising a peracid that comprises peroxyformic acid, 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 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 at least within 4 hours of said contacting.