Method for treating produced water

Abstract

The present embodiments generally relate to the treatment of produced water such as produced water resulting from an industrial process such as one involving the use of copious amounts of water and the addition of one or more polymers such as viscosifying or thickening polymers, in particular enhanced oil recovery processes or another processes resulting in polymer flooded produced water. These treatment methods include contacting the produced water with one or more reducing agents and one or more metals, wherein said treatment may result in a reduction of the viscosity of said produced water and/or the degradation of polymers which are contained therein.

1 - 79 . (canceled) 
     
     
         80 . A process for treating produced water comprising one or more water soluble polymers comprising treating the produced water with an amount of one or more reducing agents and one or more metals that is effective to reduce the viscosity of the produced water and/or to degrade at least a portion of the one or more water soluble polymers. 
     
     
         81 . The process of  claim 80 , wherein: (i) said water soluble polymers include high molecular weight polymers used in industrial processes such as enhanced oil recovery (EOR) processes and other processes wherein produced water is produced and/or treated; (ii) the treated produced water is anoxic and/or the produced water is treated in whole or part under anoxic conditions; (iii) said one or more water soluble polymers comprise oxygen; (iv) oxygen is added to said produced water, or any combination of the foregoing; wherein optionally in embodiment (iv), (1) the oxygen is added before, during, and/or after treatment of said produced water with said one or more reducing agents and said metal; (2) said oxygen is added through addition of water containing dissolved oxygen, such as by the addition of surface water; air bubbling; and/or pressurized air; (3) addition of oxygen result in a corresponding increase in the degradation of said polymer, optionally wherein the amount of added oxygen correlates to the amount of degradation; (4) addition of oxygen results in a corresponding decrease in the viscosity of the produced water optionally wherein the amount of added oxygen correlates to the reduction of viscosity or any combination of the foregoing. 
     
     
         82 . The process of  claim 80 , wherein: (i) said one or more metals comprises iron and/or a compound comprising iron, optionally in the Fe +2  form; (ii) said one or more reducing agents comprise a compound comprising metabisulfite, bisulfite, (hydrated) sulfur dioxide, and/or sulfite; (iii) said one or more reducing agents comprise hydrazine and/or its hydroxylamine derivatives and/or a mixture of sodium borohydride and bisulfate; (iv) said one or more reducing agents comprise organic sulfites such as alkyl sulfites, alkyl hydrosulfites, sulfinates, sulfoxylates, phosphites, and also oxalic or formic acid or salts of erythorbate and carbohydrazides; an oxygen scavenger, such as, but not limited to, carbohydrazide, hydroquinone, diethylhydroxylamine (DEHA), methyl ethyl ketoxime (MEKO), erythorbate; iron; the salt form of any compound that may be considered a reducing agent, such as sodium metabisulfite; and/or sodium dithionite; (v) said produced water is generated during any part of an enhanced oil recovery process; (vi) said produced water comprises one or more water soluble thickening or viscosifying polymers; (vii) said produced water comprises polymer flooded produced water; (viii) wherein treatment of the produced water with said one or more reducing agents and said metal results in a reduction in viscosity of said produced water by 10% or less, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 62% or more, or 65% or more; (ix) treatment of the produced water degrades and/or reduces the average molecular weight of said one or more water soluble polymers and/or said one or more water soluble thickening or viscosifying polymers, optionally wherein the average molecular weight of said one or more water soluble polymers and/or said one or more water soluble thickening or viscosifying polymers is lower after treatment with said one or more reducing agents and said one or more metals than the molecular weight before treatment with said one or more reducing agents and said one or more metals; (x) said process comprises treating said produced water at a temperature of 50° C. or less, 50° C. or more, 55° C. or more, 60° C. or more, 65° C. or more, 70° C. or more, 75° C. or more, 80° C. or more, 85° C. or more, 90° C. or more, 95° C. or more, or 100° C. or more; (xi) said treated produced water is reused in the same or other industrial processes; (xii) the treated produced water is used for reinjection in an industrial process; (xiii) the treated produced water is disposed of after treatment, such as released into the environment; (xiv) said treated produced water is reused for polymer injection, backflow water application, and/or water injection; (xv) said treated produced water is used for skim tank settling; (xvi) said produced water comprises one or more PAMs, such as, for example, any polymers or co-polymers comprising acrylamide moieties, one or more acrylamide (co)polymers, and/or one or more water soluble high molecular weight anionic polyacrylamide-based polymers, wherein optionally said one or more PAMs comprise one or more HPAMs and/or one or more DPAMs; (xvii) treatment of the produced water occurs on-site, at any onshore oil field, at any offshore oil field, at a treatment facility, at a disposal well, or at any other location where produced water is present and/or treated; or any combination of the foregoing. 
     
     
         83 . A process of treating produced water according to  claim 80 , that includes the addition of one or more reducing agents and one or more metals during treatment of the produced water wherein at least one stabilizing agent is added to slow, decrease, prevent, inhibit and/or stop the degradation or further degradation of water soluble polymers and/or to increase or maintain the viscosity of the produced water. 
     
     
         84 . The process of  claim 83 , wherein: (i) the at least one stabilizing agent is added while water soluble polymers are present in the produced water in order to slow, decrease, prevent, inhibit, and/or stop the degradation or further degradation of said at least one water soluble polymer and/or to increase or maintain the viscosity of the produced water; (ii) the at least one stabilizing agent is added contemporaneous or prior to the addition of at least one water soluble polymer in order to slow, decrease, prevent, inhibit, and/or stop the degradation of said added at least one water soluble polymer and/or to increase or maintain the viscosity of the produced water; (iii) said process comprises adding at least one stabilizing agent while water soluble polymers are present in the produced water in order to slow, decrease, prevent, and/or stop the degradation or further degradation of said at least one water soluble polymer comprised in the produced water and/or to increase or maintain the viscosity of the produced water; (iv) said process comprises adding an amount of at least one additional water soluble polymer contemporaneous or after the addition of the at least one stabilizing agent in order to slow, decrease, prevent, and/or stop the degradation of said further added at least one water soluble polymer and/or to increase or maintain the viscosity of the produced water; (v) said process includes the addition of at least one stabilizing agent at different times during treatment of the produced water in order to slow, decrease, prevent, and/or stop the degradation or further degradation of water soluble polymers or another material susceptible to degradation by the one or more reducing agents and one or more metals and/or to increase or maintain the viscosity of the produced water; (vi) treatment of said produced water comprises treatment of anoxic treated produced water and/or treatment under anoxic conditions; (vii) said one or more water soluble polymers comprise oxygen; (viii) said produced water comprises polymer flooded produced water; or any combination of (i) to (viii). 
     
     
         85 . The process of  claim 80 , wherein one or more stabilizing agents are added to said produced water following treatment with said one or more reducing agents and said one or more metals, and the addition of said one or more stabilizing agents optionally slows, decreases, prevents, and/or stops degradation of said one or more water soluble polymers, wherein optionally (i) said stabilizing agent comprises thiourea, diethylthiourea, sodium/ammonium thiocyanate, benzotriazole, MBI, and/or MBT; (ii) said stabilizing agent comprises a free radical scavenger; thiourea, 2-mercaptobenzothiazole, dimedone, N,N′-dimethylthiourea, N,N′-diethylthiourea, N,N′-diphenylthio urea, ammonium thiocyanate, tetramethylthiuram disulphide, 2,2′-dithiobis(benzothiazole), sodium dimethyldithiocarbarnate, paramethoxyphenol propyl, 3,4,5-trihydroxybenzoate, 2,6-di-tert-butyl-4-methylphenol, 2,5-di(tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), ammonium N-nitrosophenylhydroxylamine, butylhydroxyanisole, hydroxy-8-quinoleine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 5-hydroxy-1,4-naphtoquinone, (N-(1,3-dimethylbutyl)N′phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, 2,5-Di (tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), dicyandiamide, guanidine, and/or cyanamide; thioureas and alkyl thioureas, mercaptobenzoimidazole (MBI) or mercaptobenzothiazole (MBT) and combinations thereof, butyl hydroxyanisole, paramethoxy phenol, quinolinol, 5,5-dimethyl-1,3-cyclohexane dione, and/or sodium thiocyanate; diethyl thiourea, dimethyl thiourea, mercaptobenzothiazole and mercapto benzoimidazole; a precipitating agent such as, but not limited hydroxides, carboxylates, carbonates, arsenates, cyanurates, phosphorus derivatives and/or sulfur derivatives; phosphorus salts, sodium phosphate, sodium hydrogenophosphate, phytic acid, or of sulfur salts, sodium sulfide, sodium sulfydrate or, for the family of carbonates, sodium carbonate; sodium carbonate and/or sodium phosphate; a sacrificial agent, such as those in the family of alcohols, such as, for example, monoalcohols, polyols, glycerol, propylene glycol, trimethyleneglycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (FETA), trimethylolethane, neopentylglycol, 1, -pentanedial, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, and/or 1,5-pentanediol, polyvinyl alcohol partially or totally hydrolyzed; and/or an antioxidant; (iii) additional water soluble polymer is added following addition of said stabilizing agent, wherein optionally said new water soluble polymer is protected from degradation by said stabilizing agent; (iv) stabilizing agent is added during and/or before addition of new water soluble polymer; (v) said stabilizing agent is added after the viscosity of said treated produced water reaches a desired value; or any combination of the foregoing. 
     
     
         86 . The process of  claim 80 , wherein said process further comprises: a. treating the produced water with an amount of one or more reducing agents and one or more metals that is effective to reduce the viscosity of the produced water and/or to degrade at least a portion of the one or more water soluble polymers; b. adding an amount of stabilizer effective to slow, reduce, decrease, inhibit, prevent, and/or stop degradation of said one or more water soluble polymers; and optionally c. adding new and/or fresh water soluble polymer; wherein optionally (i) said stabilizer reduces, decreases, stops, and/or prevents degradation of said new and/or fresh water soluble polymer; (ii) treatment of said produced water comprises treatment of anoxic treated produced water and/or treatment of the produced water in whole or part under anoxic conditions; (iii) said stabilizing agent comprises thiourea, diethylthiourea, sodium/ammonium thiocyanate, benzotriazole, MBI, and/or MBT; (iv) said stabilizing agent comprises a free radical scavenger; thiourea, 2-mercaptobenzothiazole, dimedone, N,N′-dimethylthiourea, N,N′-diethylthiourea, N,N′-diphenylthio urea, ammonium thiocyanate, tetramethylthiuram disulphide, 2,2′-dithiobis(benzothiazole), sodium dimethyldithiocarbarnate, paramethoxyphenol propyl, 3,4,5-trihydroxybenzoate, 2,6-di-tert-butyl-4-methylphenol, 2,5-di(tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), ammonium N-nitrosophenylhydroxylamine, butylhydroxyanisole, hydroxy-8-quinoleine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 5-hydroxy-1,4-naphtoquinone, (N-(1,3-dimethylbutyl)N′phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, 2,5-Di (tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), dicyandiamide, guanidine, and/or cyanamide; thioureas and alkyl thioureas, mercaptobenzoimidazole (MBI) or mercaptobenzothiazole (MBT) and combinations thereof, butyl hydroxyanisole, paramethoxy phenol, quinolinol, 5,5-dimethyl-1,3-cyclohexane dione, and/or sodium thiocyanate; diethyl thiourea, dimethyl thiourea, mercaptobenzothiazole and mercapto benzoimidazole; a precipitating agent such as, but not limited hydroxides, carboxylates, carbonates, arsenates, cyanurates, phosphorus derivatives and/or sulfur derivatives; phosphorus salts, sodium phosphate, sodium hydrogenophosphate, phytic acid, or of sulfur salts, sodium sulfide, sodium sulfydrate or, for the family of carbonates, sodium carbonate; sodium carbonate and/or sodium phosphate; a sacrificial agent, such as those in the family of alcohols, such as, for example, monoalcohols, polyols, glycerol, propylene glycol, trimethyleneglycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (FETA), trimethylolethane, neopentylglycol, 1, -pentanedial, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, and/or 1,5-pentanediol, polyvinyl alcohol partially or totally hydrolyzed; and/or an antioxidant or any combination of the foregoing. 
     
     
         87 . The process of  claim 86 , wherein: (i) stabilizing agent is added during and/or before addition of new water soluble polymer; (ii) stabilizing agent is added after the viscosity of said treated produced water reaches a desired value; (iii) said one or more metals comprises iron and/or a compound comprising iron, optionally in the Fe +2  form; (iv) said one or more reducing agents comprise a compound comprising metabisulfite, bisulfite, (hydrated) sulfur dioxide, and/or sulfite; (v) said one or more reducing agents comprise hydrazine and/or its hydroxylamine derivatives and/or a mixture of sodium borohydride and bisulfate; (vi) said one or more reducing agents comprise organic sulfites such as alkyl sulfites, alkyl hydrosulfites, sulfinates, sulfoxylates, phosphites, and also oxalic or formic acid or salts of erythorbate and carbohydrazides; an oxygen scavenger, such as, but not limited to, carbohydrazide, hydroquinone, diethylhydroxylamine (DEHA), methyl ethyl ketoxime (MEKO), erythorbate; iron; the salt form of any compound that may be considered a reducing agent, such as sodium metabisulfite; and/or sodium dithionite; (vii) said produced water is generated during any part of an enhanced oil recovery process; (viii) said produced water comprises one or more water soluble thickening or viscosifying polymers; (ix) said produced water comprises polymer flooded produced water; (x) said treated produced water is reused in the same or other industrial processes or released into the environment; (xi) treatment of the produced water with said one or more reducing agents and said one or more metals is beneficial for reinjection or disposal purposes; (xii) the treated produced water is used for reinjection or disposal purposes; (xiii) said treated produced water is reused for polymer injection, backflow water application, and/or water injection; (xiv) the treated produced water is more effective in skim tank settling compared to the untreated produced water; (xv) the treated produced water is used for skim tank settling; (xvi) treatment of the produced water occurs on-site, at any onshore oil field, at any offshore oil field, at a treatment facility, at a disposal well, or at any other location where produced water is present or treated; or any combination of the foregoing. 
     
     
         88 . A composition suitable for use in treating produced water, comprising the combination of (i) one or more stabilizing agents and either or both of the following: (ii) one or more reducing agents and one or more metals, and (iii) one or more water soluble polymers; wherein the one or more stabilizing agents are capable of preventing or inhibiting the degradation of (iii) one or more water soluble polymer by the (ii) one or more reducing agents and one or more metals if said (iii) one or more water soluble present. 
     
     
         89 . The composition of  claim 88 , wherein: (1) it comprises (i) one or more stabilizing agents, (ii) one or more reducing agents and one or more metals, and (iii) one or more water soluble polymers; (2) it is suitable for treating anoxic treated produced water and/or produced water under anoxic conditions; (3) said one or more water soluble polymers comprise oxygen; (4) oxygen is added to said composition; (5) it is suitable for treating produced water wherein oxygen is added before, during, and/or after treatment of said produced water with said one or more reducing agents and said metal, optionally wherein said oxygen is added through addition of water containing dissolved oxygen, such as the addition of surface water; air bubbling; and/or pressurized air; (6) it is suitable for treating produced water wherein oxygen is added before, during, and/or after treatment of said produced water through addition of water containing dissolved oxygen, such as the addition of surface water; air bubbling; and/or pressurized air; (7) said one or more metals comprises iron and/or a compound comprising iron, optionally in the Fe +2  form; (8) said one or more reducing agents comprise a compound comprising metabisulfite, bisulfite, (hydrated) sulfur dioxide, and/or sulfite; (9) said produced water comprises one or more PAMs, such as, for example any polymers or co-polymers comprising acrylamide moieties, one or more acrylamide (co)polymers and/or one or more water soluble high molecular weight anionic polyacrylamide-based polymers, optionally wherein said one or more PAMs comprise one or more HPAMs and/or one or more DPAMs; (10) said produced water comprises polymer flooded produced water; (11) said stabilizing agent comprises thiourea, diethylthiourea, sodium/ammonium thiocyanate, benzotriazole, MBI, and/or MBT; (12) said stabilizing agent comprises a free radical scavenger; thiourea, 2-mercaptobenzothiazole, dimedone, N,N′-dimethylthiourea, N,N′-diethylthiourea, N,N′-diphenylthio urea, ammonium thiocyanate, tetramethylthiuram disulphide, 2,2′-dithiobis(benzothiazole), sodium dimethyldithiocarbarnate, paramethoxyphenol propyl, 3,4,5-trihydroxybenzoate, 2,6-di-tert-butyl-4-methylphenol, 2,5-di(tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), ammonium N-nitrosophenylhydroxylamine, butylhydroxyanisole, hydroxy-8-quinoleine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 5-hydroxy-1,4-naphtoquinone, (N-(1,3-dimethylbutyl)N′phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, 2,5-Di (tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), dicyandiamide, guanidine, and/or cyanamide; thioureas and alkyl thioureas, mercaptobenzoimidazole (MBI) or mercaptobenzothiazole (MBT) and combinations thereof, butyl hydroxyanisole, paramethoxy phenol, quinolinol, 5,5-dimethyl-1,3-cyclohexane dione, and/or sodium thiocyanate; diethyl thiourea, dimethyl thiourea, mercaptobenzothiazole and mercapto benzoimidazole; a precipitating agent such as, but not limited hydroxides, carboxylates, carbonates, arsenates, cyanurates, phosphorus derivatives and/or sulfur derivatives; phosphorus salts, sodium phosphate, sodium hydrogenophosphate, phytic acid, or of sulfur salts, sodium sulfide, sodium sulfydrate or, for the family of carbonates, sodium carbonate; sodium carbonate and/or sodium phosphate; a sacrificial agent, such as those in the family of alcohols, such as, for example, monoalcohols, polyols, glycerol, propylene glycol, trimethyleneglycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (FETA), trimethylolethane, neopentylglycol, 1, -pentanedial, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, and/or 1,5-pentanediol, polyvinyl alcohol partially or totally hydrolyzed; and/or an antioxidant or any combination of the foregoing. 
     
     
         90 . A produced water composition comprising one or more water soluble polymers to which has been added a composition according to  claim 88 , in an amount effective to reduce the viscosity of the produced water and/or to degrade at least a portion of the one or more water soluble polymers therein. 
     
     
         91 . produced water composition comprising one or more water soluble polymers to which has been added a composition according to  claim 89 , in an amount effective to reduce the viscosity of the produced water and/or to degrade at least a portion of the one or more water soluble polymers therein. 
     
     
         92 . A produced water composition comprising one or more water soluble high molecular weight polymers used for enhanced oil recovery (EOR) or polymer flooding, optionally one or more polyacrylamides (PAMs), which comprises (1) an amount of one or more reducing agents and (2) iron and/or a compound comprising iron in the Fe +2  form, wherein the amounts of (1) and (2) in combination are sufficient to reduce the viscosity of the produced water and/or to degrade a portion of said one or more water soluble polymers therein. 
     
     
         93 . The produced water composition of  claim 92 , which is anoxic. 
     
     
         94 . The produced water composition of  claim 92 , which is produced during a polymer flooding process or is generated during any part of an enhanced oil recovery process. 
     
     
         95 . The produced water composition of  claim 92 , wherein said one or more water soluble polymers comprise (i) polymers or co-polymers comprising acrylamide moieties, one or more acrylamide (co)polymers, and/or one or more water soluble high molecular weight anionic polyacrylamide-based polymers; (ii) high molecular weight polyacrylamide and/or copolymers of acrylamide and one or more other monomers, (iii) partly hydrolyzed polyacrylamide (“HPAM”) in which some of the acrylamide units have been hydrolyzed to acrylic acid, (iv) high molecular weight anionic polyacrylamide based polymers, (v) naturally occurring polymers, (vi) xanthan or polyglycosylglucan polymers, or (vii) any combination of the foregoing. 
     
     
         96 . The produced water composition of  claim 92 , wherein said one or more reducing agents comprise (i) a compound comprising metabisulfite, bisulfite, (hydrated) sulfur dioxide, and/or sulfite, (ii) hydrazine and/or its hydroxylamine derivatives and/or a mixture of sodium borohydride and bisulfite, (iii) at least one organic sulfite, (iv) alkyl sulfites, alkyl hydrosulfites, sulfinates, sulfoxylates, phosphites, oxalic or formic acid or salts of erythorbate and carbohydrazides; (v) oxygen scavengers, (vi) carbohydrazide, hydroquinone, diethylhydroxylamine (DEHA), methyl ethyl ketoxime (MEKO), erythorbate; sodium metabisulfite, sodium dithionite or (vii) any combination of the foregoing and preferably said one or more reducing agents comprise a metabisulfite, bisulfite, (hydrated) sulfur dioxide, and/or sulfite compound. 
     
     
         97 . The produced water composition of  claim 92 , wherein said one or more reducing agents result in the production of HSO 3   − . 
     
     
         98 . The produced water composition of  claim 92 , which further comprises at least one stabilizing agent which further slows or arrests the degradation of water soluble polymers comprised in the treated produced water and/or increases or maintains the viscosity of the treated produced water. 
     
     
         99 . The produced water composition of  claim 98 , wherein said stabilizing agent comprises (i) thiourea, diethylthiourea, sodium/ammonium thiocyanate, benzotriazole, MBI, and/or MBT; (ii) a free radical scavenger; thiourea, 2-mercaptobenzothiazole, dimedone, N,N′-dimethylthiourea, N,N′-diethylthiourea, N,N′-diphenylthio urea, ammonium thiocyanate, tetramethylthiuram disulphide, 2,2′-dithiobis(benzothiazole), sodium dimethyldithiocarbarnate, paramethoxyphenol propyl, 3,4,5-trihydroxybenzoate, 2,6-di-tert-butyl-4-methylphenol, 2,5-di(tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), ammonium N-nitrosophenylhydroxylamine, butylhydroxyanisole, hydroxy-8-quinoleine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 5-hydroxy-1,4-naphtoquinone, (N-(1,3-dimethylbutyl)N′phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, 2,5-Di (tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), dicyandiamide, guanidine, and/or cyanamide; thioureas and alkyl thioureas, mercaptobenzoimidazole (MBI) or mercaptobenzothiazole (MBT) and combinations thereof, butyl hydroxyanisole, paramethoxy phenol, quinolinol, 5,5-dimethyl-1,3-cyclohexane dione, and/or sodium thiocyanate; diethyl thiourea, dimethyl thiourea, mercaptobenzothiazole and mercapto benzoimidazole; a precipitating agent, a precipitating agent selected from hydroxides, carboxylates, carbonates, arsenates, cyanurates, phosphorus derivatives and/or sulfur derivatives; phosphorus salts, sodium phosphate, sodium hydrogenophosphate, phytic acid, sulfur salts, sodium sulfide, sodium sulfydrate, sodium carbonate; sodium carbonate and/or sodium phosphate; a sacrificial agent, monoalcohols, polyols, glycerol, propylene glycol, trimethyleneglycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (FETA), trimethylolethane, neopentylglycol, 1, -pentanedial, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, and/or 1,5-pentanediol, polyvinyl alcohol partially or totally hydrolyzed; and/or an antioxidant or said stabilizing agent comprises (i) thiourea, diethylthiourea, sodium/ammonium thiocyanate, benzotriazole, MBI, and/or MBT; (ii) a free radical scavenger; thiourea, 2-mercaptobenzothiazole, dimedone, N,N′-dimethylthiourea, N,N′-diethylthiourea, N,N′-diphenylthio urea, ammonium thiocyanate, tetramethylthiuram disulphide, 2,2′-dithiobis(benzothiazole), sodium dimethyldithiocarbarnate, paramethoxyphenol propyl, 3,4,5-trihydroxybenzoate, 2,6-di-tert-butyl-4-methylphenol, 2,5-di(tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), ammonium N-nitrosophenylhydroxylamine, butylhydroxyanisole, hydroxy-8-quinoleine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy, 5-hydroxy-1,4-naphtoquinone, (N-(1,3-dimethylbutyl)N′phenyl-p-phenylenediamine, 2,6-di-tert-butyl-4-methylphenol, 2,5-Di (tert-amyl) hydroquinone, 4,4′-thiobis(6-tert-butyl-m-cresol), dicyandiamide, guanidine, and/or cyanamide; thioureas and alkyl thioureas, mercaptobenzoimidazole (MBI) or mercaptobenzothiazole (MBT) and combinations thereof, butyl hydroxyanisole, paramethoxy phenol, quinolinol, 5,5-dimethyl-1,3-cyclohexane dione, and/or sodium thiocyanate; diethyl thiourea, dimethyl thiourea, mercaptobenzothiazole and mercapto benzoimidazole; a precipitating agent, a precipitating agent selected from hydroxides, carboxylates, carbonates, arsenates, cyanurates, phosphorus derivatives and/or sulfur derivatives; phosphorus salts, sodium phosphate, sodium hydrogenophosphate, phytic acid, sulfur salts, sodium sulfide, sodium sulfydrate, sodium carbonate; sodium carbonate and/or sodium phosphate; a sacrificial agent, monoalcohols, polyols, glycerol, propylene glycol, trimethyleneglycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (FETA), trimethylolethane, neopentylglycol, 1, -pentanedial, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, and/or 1,5-pentanediol, polyvinyl alcohol partially or totally hydrolyzed; and/or an antioxidant.