Method for the in-situ generation chlorine dioxide

Abstract

The invention relates to the in-situ generation of chlorine dioxide for the treatment of hydrocarbon processing systems. The composition comprises a source of chlorite, a source of persulfate and water. Under the specified conditions of temperature and/or halide catalyst, chlorine dioxide is generated at an increased rate, thereby effectively treating down-hole hydrocarbon recovery systems.

I claim: 
     
         1 . A method for the in-situ generation of chlorine dioxide in hydrocarbon recovery systems, said method comprising the steps of combining a source of chlorite, a source of persulfate and water to form a composition; the molar ratio of chlorite (having the general formula ClO 2   − ) to persulfate (having the general formula S 2 O 8   ═ ) being greater than 0.5:1; introducing said composition into a hydrocarbon recovery system; achieving a temperature of greater than 100° F., and wherein all or part of the chlorite is converted to chlorine dioxide within the hydrocarbon recovery system. 
     
     
         2 . The method of  claim 1 , wherein said hydrocarbon recovery system is selected from the group consisting of geological material that contains one or more solid, liquid, or gaseous hydrocarbons, a hydrocarbon deposit, a petroleum deposit, a hydrocarbon or petroleum product formation, and a hydrocarbon or petroleum processing product or equipment, or combinations thereof. 
     
     
         3 . The method of  claim 2 , wherein the hydrocarbon or petroleum processing product or equipment is selected from the group consisting of one or more pieces of equipment for extracting, processing, or refining hydrocarbons, a pipeline for transporting hydrocarbons and a vessel for storage of hydrocarbons. 
     
     
         4 . The method of  claim 1 , wherein the molar ratio of chlorite to persulfate is great than or equal to 1:1. 
     
     
         5 . The method of  claim 1 , wherein the molar ratio of chlorite to persulfate is greater than or equal to 2:1. 
     
     
         5 . The method of  claim 1 , wherein the chlorine dioxide is sufficient to reduce, inactivate, destroy, or eliminate at least one or more reducing agents, polymers or microbes in the hydrocarbon recovery system. 
     
     
         6 . The method of  claim 1 , wherein the composition is in sufficient amount to perform well remediation. 
     
     
         7 . The method of  claim 1 , wherein the hydrocarbon recovery system further comprises formation fluid having a catalytically effective amount of halide. 
     
     
         8 . The method of  claim 7 , wherein the catalytically effective amount of halide is selected from at least one of bromide and chloride anions. 
     
     
         8 . The method of  claim 1 , wherein the source of chlorite comprises chlorine dioxide. 
     
     
         9 . The method of  claim 1 , wherein the source of chlorite is sodium chlorite. 
     
     
         10 . The method of  claim 1 , wherein the source of persulfate is selected from at least one of sodium or potassium persulfate. 
     
     
         11 . The method of  claim 1 , wherein the source of persulfate is selected from ammonium persulfate. 
     
     
         12 . The method of  7 , wherein the catalytically effective amount of halide is bromide. 
     
     
         13 . The method of  claim 1 , wherein the source of chlorite is in an aqueous solution. 
     
     
         14 . The method of  claim 1 , wherein the source of persulfate is in an aqueous solution. 
     
     
         15 . The method of  claim 1 , wherein the source of chlorite is in a solid form. 
     
     
         16 . The method of  claim 1 , wherein the source of persulfate is in a solid form. 
     
     
         17 . The method of  claim 1 , wherein the composition further comprises at least one additive selected from at least one hydrotrope, surfactant, dispersant, chelant, sequestrant, and acid. 
     
     
         18 . The method of  claim 17 , wherein the additive is a phosphate ester comprising (a) a hydrophilic polyoxyethylene chain having a range of PEO-3 to PEO-9 and an R-terminal group selected from the group consisting of a lipophilic alkyl chain having a range of C9 to C13 and a nonylphenol; (b) ethoxylated polyarylphenol phosphate having a polyoxyethylene chain of POE-16, and (c) a phosphate ester comprising an alkylphenoxy polyethoxyethanol.